JP2021523905A - Total synthesis of prostaglandin J natural products by three-dimensional retention metathesis - Google Patents

Abstract

The present invention generally relates to the synthesis of Δ12-prostaglandin J products using a conformational ruthenium olefin metathesis catalyst supported by a dithiolate ligand. The Δ12-prostaglandin J product has excellent selectivity (> 99% Z) and moderate to high / good yields (47% -80% yield, 58% -80% yield). Generated with it.

Description

(Statement of Federally Supported Research or Development)
The present invention was made with the government support of NIH Grant No. GM031332. The US Government has certain rights in the present invention.

(Related application)
This application is the benefit of US Provisional Patent Application No. 62 / 671,891 filed May 15, 2018, and US Provisional Patent Application No. 62 / 803,603 filed February 11, 2019. Is made by reference in its entirety, which is incorporated herein by reference.

(Field of invention)
Prostaglandins are an important class of naturally occurring molecules found in mammalian tissues and exhibiting a wide range of biological functions and a wide range of medical uses. [Marks F. and Furstenberger G.M. Prostaglandins, Laukotrienes and Other Eicosanoids; Wiley-Blackwell, 1999. Funk, C.I. D. Prostaglandins and Leukotrienes: Advances in Eicosanoid Biology. Science 2001,294,1871-1875. ]

Efforts towards the synthesis of various prostaglandins have a profound effect on the development of new strategies and tactics adopted in the field of synthetic chemistry, starting with Corey's original research that began in the 1960s. Issue. [Corey, E.I. J. Weinschenker, N. et al. M. Schaf, T. et al. K. Huber, W. et al. Stereo-Control Synthesis of Dl-Prostaglandins F2. alpha. and E2. J. Am. Chem. Soc. 1969, 91, 5675-5677. Das, S.M. Chandrasekhar, S.A. Yadav, J. et al. S. Gree, R.M. Recent Developments in the Synthesis of Prostaglandins and Analogues. Chem. Rev. 2007,107,3286-3337. Peng, H. et al. Chen, F. et al. -E. Recent Advances in Asymmetry Total Synthesis of Prostaglandins. Org. Biomol. Chem. 2017,15,6281-6301. ]

As shown in FIG. 1, recently discovered delta ^{12 -} prostaglandin J Group (1), (2), (3), and (4), the specific cross-conjugated diene motifs and attractive anti It is characterized by cancer activity. [Straus D. S. Glass C.I. K. Cyclopentenone Prostaglandins: New Insights on Biological Activities and Cellular Targets. Med. Res. Rev. 2001, 21, 185-210. ]

For example, Δ ¹² -PGJ 3 ₍₃₎ is isolated as a secondary metabolite, to selectively induce apoptosis of leukemic stem cells on normal hematopoietic stem cells with high potency was shown. [Hegde, S.M. Kaushal, N. et al. Kaushal, N. et al. Chiaro, C.I. Hafer, K. et al. T. Gandhi, U.S.A. H. Thompson, J. et al. T. Van den Heuvel, J. et al. P. Kennett, M. et al. J. Hankey, P.M. Paulson R.M. F. Prabhu K.K. S. Δ ^12- Prostaglandin J ₃ , an Omega-3 Fatty Acid-Delivered Metabolite, Selectively Ablates Leukemia Stem Cells in Machine. Blood 2011, 118, 6909-6919. ]

Its stability, studies of bioavailability, and hypersensitivity, the Δ ¹² -PGJ ₃ and interesting drug candidate for the treatment of leukemia. [Kudva, A. K. Kaushal, N. et al. Mohinta, S. et al. Kennett, M. et al. J. August, A. et al. Paulson, R. et al. F. Prabhu, K. et al. S. Evaluation of the Stability, Bioavailability, and Hypersensitivity of the Omega-3 Derived Anti-Leukemic Prostaglandin: Δ 12 -Prostaglandin J 3 PLOS ONE 2013,8, e80622. ]

It reported through various approaches, using a number of synthetic Δ ¹² -PGJ ₂ (1) and _15d-PGJ 2 (2), 2003, delta ¹² - synthesis approach to prostaglandin _{J 2} Compound Started. [Bickley, J. et al. F. Jadhave, V.I. Roberts, S.A. M. Santaro, M. et al. G. Steiner, A.M. Sutton, P. et al. W. Synthesis of Optically Active Prostaglandin J ₂ and 15-Deoxy-Δ ^{12, 14} Prostaglandin J ₂ . Synlett 2003, 1170-1174. Brummondo, K. et al. M. Sill, P. et al. C. Chen, H. et al. The First Total Synthesis of 15-Deoxy-Δ ^12,14- Prostaglandin J ₂ and the Unambiguous Assignment of the C14 Stereochemistry. Org. Lett. 2004, 6, 149-152. Acharya, H. et al. P. Kobayashi, Y. et al. Total Synthesis of Δ ^12- PGJ ₂ , 15-Deoxy-Δ ^{12, 14-} PGJ ₂ , and Related Compounds. Tetrahedron Letter. 2004, 45, 1199-1202. Acharya, H. et al. P. Kobayashi, Y. et al. Highly Effective Total Synthesis of Δ ^12- _{PGJ 2} , 15-Deoxy-Δ ^{12, 14-} PGJ ₂ , and Their Analogues. Tetrahedron 2006, 62, 3329-3343. Kim, N.M. -J. Moon, H. et al. Park, T. et al. Yun, H. et al. Jung, J. et al. -W. Chang, D.C. -J. Kim, D.I. -D. Shu, Y. et al. -G. Concise and Enantioselective Total Synthesis of 15-Deoxy-Δ ^{12, 14-} Prostaglandin J ₂ J. et al. Org. Chem. 2010, 75, 7458-7460. Egger, J. et al. Fischer, S.A. Brettcher, P. et al. Freigan, S.A. Kopf, M. et al. Carreira, E.I. M. Total Synthesis of Prostaglandin 15d-PGJ ₂ and Investment of Its Effect on the Selection of IL-6 and IL-12. Org. Lett. 2015, 17, 4340-4343. ]

The ^{spectacular contribution of Δ 12-} PGJ ₃ (3) to the total synthesis was reported by Nicolaou and co-workers, and more recently by the Aggarwal group. [Nicolaou, K. C. Heretsch, P. et al. El Marroni, A. et al. Hale, C.I. R. H. Pulukuri, K. et al. K. Kudva, A.M. K. Narayan, V. et al. Prabhu, K. et al. S. Total Synthesis of Δ ^12- Prostaglandin J ₃ , a Highly Potent and Selective Active Agent. Angew. Chem. Int. Ed. 2014,53,10443-10447. Nicolaou, K. Nicola C. Pulukuri, K. et al. K. Yu, R.M. Rigol, S. et al. Heretsch, P. et al. Grove, C.I. I. Hale, C.I. R. H. El Marroni, A. et al. Total Synthesis of Δ ^12- Prostaglandin J ₃ : Evolution of Synthetic Strategies to a Streamlined Process. Chem. -Eur. J. 2016, 22, 8559-8570. Pelshs, A. et al. Gandhamsetti, N. et al. Smith, J. et al. R. Mailhol, D.M. Silvi, M. et al. Watson, A. et al. J. A. Perez-Powerell, I. et al. Prevost, S.M. Schutzenmeister, N. et al. Moore, P.M. R. Aggarwal V.I. K. Reoptimization of the Organocatalyzed Double Aldol Domino Process to a Key Enal Intermediate and Its Application to the Total Synthesis of Δ 12 -Prostaglandin J 3 Chem. -Eur. J. 2018, 24, 9542-9545. ]

Some Δ ¹² -PGJ ₃ analogs also are also available by streamlining synthesis developed by Nicolaou and coworkers, comprehensive structure activity relationship of these anti-cancer activity (SAR) studies Made possible. [Nicolaou, K. C. Pulukuri, K. et al. K. Rigol, S. et al. Heretsch, P. et al. Yu, R.M. Grove, C.I. I. Hale, C.I. R. H. El Marroni, A. et al. Fets, V.I. Bronstrup, M. et al. Aujay M.M. Sandoval J. et al. Gavrilliuk J. et al. Synthesis and Biological ^{Investment of Δ 12-} Prostaglandin J ₃ (Δ ^12- PGJ ₃ ) Analogues and Reserved Compounds. J. Am. Chem. Soc. 2016, 138, 6550-6560. ]

Hegde, S.M. Kaushal, N. et al. Kaushal, N. et al. Chiaro, C.I. Hafer, K. et al. T. Gandhi, U.S.A. H. Thompson, J. et al. T. Van den Heuvel, J. et al. P. Kennett, M. et al. J. Hankey, P.M. Paulson R.M. F. Prabhu K.K. S. Δ12-Prostaglandin J3, an Omega-3 Fatty Acid-Derived Metabolite, Selectively Ablates Leukemia Stem Cells in Machine. Blood 2011, 118, 6909-6919 Kudva, A.M. K. Kaushal, N. et al. Mohinta, S. et al. Kennett, M. et al. J. August, A. et al. Paulson, R. et al. F. Prabhu, K. et al. S. Assessment of the Stability, Bioavailability, and Hypersensitivity of the Omega-3 Dived Anti-Leukemic Prostaglandin: Δ12-Prostaglandin, Δ12-Prostaglandin, Δ12-Prostaglandin, Bickley, J. et al. F. Jadhave, V.I. Roberts, S.A. M. Santaro, M. et al. G. Steiner, A.M. Sutton, P. et al. W. Synthesis of Optically Active Prostaglandin J2 and 15-Deoxy-Δ12, 14 Prostaglandin J2. Synlett 2003, 1170-1174 Brummondo, K. et al. M. Sill, P. et al. C. Chen, H. et al. The First Total Synthesis of 15-Deoxy-Δ12, 14-Prostaglandin J2 and the Unambiguous Assignment of the C14 Stereochemistry. Org. Lett. 2004, 6, 149-152 Acharya, H. et al. P. Kobayashi, Y. et al. Total Synthesis of Δ12-PGJ2,15-Deoxy-Δ12, 14-PGJ2, and Reserved Compounds. Tetrahedron Letter. 2004, 45, 1199-1202 Acharya, H. et al. P. Kobayashi, Y. et al. Highly Effective Total Synthesis of Δ12-PGJ2,15-Deoxy-Δ12, 14-PGJ2, and Their Analogues. Tetrahedron 2006, 62, 3329-3343 Kim, N.M. -J. Moon, H. et al. Park, T. et al. Yun, H. et al. Jung, J. et al. -W. Chang, D.C. -J. Kim, D.I. -D. Shu, Y. et al. -G. Concise and Enantioselective Total Synthesis of 15-Deoxy-Δ12, 14-Prostaglandin J2 J. Org. Chem. 2010,75,7458-7460 Egger, J. et al. Fischer, S.A. Brettcher, P. et al. Freigan, S.A. Kopf, M. et al. Carreira, E.I. M. Total Synthesis of Prostaglandin 15d-PGJ2 and Investment of Its Effect on the Selection of IL-6 and IL-12. Org. Lett. 2015, 17, 4340-4343 Nicolaou, K. Nicola C. Heretsch, P. et al. El Marroni, A. et al. Hale, C.I. R. H. Pulukuri, K. et al. K. Kudva, A.M. K. Narayan, V. et al. Prabhu, K. et al. S. Total Synthesis of Δ12-Prostaglandin J3, a Highly Potent and Selective Antileukemic Agent. Angew. Chem. Int. Ed. 2014,53,10443-10447 Nicolaou, K. Nicola C. Pulukuri, K. et al. K. Yu, R.M. Rigol, S. et al. Heretsch, P. et al. Grove, C.I. I. Hale, C.I. R. H. El Marroni, A. et al. Total Synthesis of Δ12-Prostaglandin J3: Evolution of Synthetic Strategies to a Streamlined Process. Chem. -Eur. J. 2016, 22, 8559-8570 Pelshs, A. et al. Gandhamsetti, N. et al. Smith, J. et al. R. Mailhol, D.M. Silvi, M. et al. Watson, A. et al. J. A. Perez-Powerell, I. et al. Prevost, S.M. Schutzenmeister, N. et al. Moore, P.M. R. Aggarwal V.I. K. Reoptimization of the Organization of The Organization -Eur. J. 2018, 24, 9542-9545 Nicolaou, K. Nicola C. Pulukuri, K. et al. K. Rigol, S. et al. Heretsch, P. et al. Yu, R.M. Grove, C.I. I. Hale, C.I. R. H. El Marroni, A. et al. Fets, V.I. Bronstrup, M. et al. Aujay M.M. Sandoval J. et al. Gavrilliuk J. et al. Synthesis and Biological Investigation of Δ12-Prostaglandin J3 (Δ12-PGJ3) Analogues and Related Compounds. J. Am. Chem. Soc. 2016,138,6550-6560

Terms and Definitions The present invention is not limited to specific reagents, reaction conditions, etc., unless otherwise specified. Because these can vary. It should also be understood that the terminology used herein is to describe a particular embodiment and should not be construed as limiting.

As used herein and in the appended claims, the singular forms such as "one (a)", "one (an)" and "the" are clearly other in content. Includes multiple objects, except where it makes sense. Thus, for example, reference to a "substituent" includes a single substituent, two or more substituents, and the like.

As used herein and in the appended claims, "for example," "for instance," "such as," or "including / including." The term ")" is intended to introduce an example to further clarify more comprehensive specifics. Unless otherwise stated, these examples are given solely to aid in the understanding of the present invention and are not intended to be limited in any way.

Some terms are mentioned in this specification and in the claims below, and these terms should be defined as having meanings as described herein.

The term "alkyl" as used herein is a linear, branched, or cyclic saturated hydrocarbon group, typically not required, but 1 to 24 carbons. Those containing atoms, preferably those containing 1 to 12 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (Pr or n-Pr), isopropyl (i-Pr), n- Included are butyl (Bu or n-Bu), isobutyl (i-Bu), t-butyl (t-Bu), octyl (Oct), decyl and the like, as well as cycloalkyl groups such as cyclopentyl (Cp) and cyclohexyl (Cy). Be done. Generally, and not necessarily, the alkyl groups herein contain 1 to about 8 carbon atoms. The term "lower alkyl" refers to an alkyl group containing 1 to 6 carbon atoms, and the specific term "cycloalkyl" refers to a cyclic alkyl group, typically 3 to 8, preferably 5. Refers to those containing ~ 7 carbon atoms. The term "substituted alkyl" refers to an alkyl substituted with one or more substituents, and the terms "heteroatom-containing alkyl" and "heteroalkyl" are alkyls in which at least one carbon atom is replaced by a heteroatom. Point to. Unless otherwise indicated, the terms "alkyl" and "lower alkyl" include linear, branched chain, cyclic, unsubstituted, substituted and / or heteroatom-containing alkyl and lower alkyl, respectively.

As used herein, the term "alkylene" refers to a bifunctional linear, branched, or cyclic alkyl group, where "alkyl" is as defined above.

The term "alkenyl" as used herein refers to a linear, branched, or cyclic hydrocarbon group containing 2 to 24 carbon atoms and containing at least one double bond. For example, it refers to ethenyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl and the like. Preferred alkenyl groups herein contain 2-12 carbon atoms. The term "lower alkenyl" refers to an alkenyl group containing 2 to 6 carbon atoms, and the specific term "cycloalkenyl" has a cyclic alkenyl group, preferably 3 to 8 carbon atoms. Refers to things. The term "substituted alkenyl" refers to an alkenyl substituted with one or more substituents, and the terms "heteroatom-containing alkenyl" and "heteroalkenyl" are alkenyl in which at least one carbon atom is replaced with a heteroatom. Point to. Unless otherwise indicated, the terms "alkenyl" and "lower alkenyl" include linear, branched chain, cyclic, unsubstituted, substituted and / or heteroatom-containing alkenyl and lower alkenyl, respectively.

The term "alkenylene" as used herein refers to a bifunctional straight chain, branched chain, or cyclic alkenyl group, where "alkenyl" is as defined above.

The term "alkynyl" as used herein refers to a straight or branched hydrocarbon group of 2 to 24 carbon atoms containing at least one triple bond, eg, ethynyl, n. -Refers to propynyl and the like. Preferred alkynyl groups herein contain 2-12 carbon atoms. The term "lower alkynyl" contains an alkynyl group containing 2 to 6 carbon atoms. The term "substituted alkynyl" refers to an alkynyl substituted with one or more substituents, and the terms "heteroatom-containing alkynyl" and "heteroalkynyl" refer to an alkynyl in which at least one carbon atom has been replaced with a heteroatom. Point to. Unless otherwise indicated, the terms "alkynyl" and "lower alkynyl" include straight chain, branched chain, unsubstituted, substituted and / or heteroatom-containing alkynyl and lower alkynyl, respectively.

As used herein, the term "alkynylene" refers to a bifunctional alkynyl group, where "alkynyl" is as defined above.

The term "alkoxy" as used herein refers to an alkyl group attached via a single terminal ether bond. That is, the "alkoxy" group can be represented as -O-alkyl, which is as defined above. A "lower alkoxy" group refers to an alkoxy group containing 1 to 6 carbon atoms. Similarly, "alkenyloxy" and "lower alkynoxy" refer to an alkenyl group and a lower alkenyl group bonded via a single terminal ether bond, respectively, and "alkynyloxy" and "lower alkynyloxy" respectively. , Refers to alkynyl groups and lower alkynyl groups attached via a single terminal ether bond.

As used herein, the term "aryl" is an aromatic substituent containing a single aromatic ring, or is directly or indirectly attached (unless otherwise specified). Aromatic substituents containing multiple fused aromatic rings, such as different aromatic rings attached to a common group such as a methylene moiety or an ethylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 6 to 10 carbon atoms. An exemplary "aryl" group contains one aromatic ring or two fused or bonded aromatic rings, such as phenyl (Ph), naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, phenanthryl and the like. As described in more detail herein, "substituted aryl" refers to an aryl moiety substituted with one or more substituents, and the terms "heteroatom-containing aryl" and "heteroaryl" are at least one. Refers to an aryl substituent in which a heteroatom is replaced with a heteroatom.

The term "aryloxy" as used herein refers to an aryl group attached via a single terminal ether bond, where "aryl" is as defined above. The "aryloxy" group can be represented as -O-aryl, where aryl is as defined above. Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 6 to 10 carbon atoms. Examples of aryloxy groups include, but are not limited to, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, Examples thereof include 2,4-dimethoxy-phenoxy and 3,4,5-trimethoxy-phenoxy.

The term "alkali" refers to an aryl group having an alkyl substituent, the term "aralkyl" refers to an alkyl group having an aryl substituent, and "aryl" and "alkyl" are as defined above. be. Preferred alkaline and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkalil and aralkyl groups contain 6 to 16 carbon atoms. Examples of the alkaline group include p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene and the like. However, it is not limited to these. Examples of aralkyl groups include, but are not limited to, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenyl. Cyclohexylmethyl, 4-benzylcyclohexylmethyl and the like can be mentioned. The terms "alkaliluoxy" and "aralkyloxy" refer to substituents of formula-OR, where R is alkalil or aralkyl, as defined, respectively.

The term "acyl" refers to the formula-(CO) -alkyl-, (CO) -aryl,-(CO) -aralkyl,-(CO) -alkalyl,-(CO) -alkenyl, or-(CO) -alkynyl. The term "acyloxy" refers to a substituent having a Refers to a substituent having CO) -alkenyl or-(CO) -alkynyl, where "alkyl", "aryl", "aralkyl", "alkalyl", "alkenyl", and "alkynyl" are defined above. That's right. The acetoxy group (-O (CO) CH ₃ , often abbreviated as -OAc) is a common example of an acyloxy group.

The terms "cyclic" and "ring" refer to alicyclic or aromatic groups, which may or may not be substituted and / or may or may not contain heteroatoms. It may be monocyclic, bicyclic, or polycyclic. The term "alicyclic" is used in the conventional sense to refer to an alicyclic cyclic portion as opposed to an aromatic cyclic moiety, which is monocyclic, bicyclic, or polycyclic. It may be.

The term "polycyclic ring" refers to an alicyclic or aromatic group, which may or may not be substituted and / or is linked or crosslinked via a single bond. Has at least two closed rings. Examples of the polycyclic ring include, but are not limited to, naphthyl, biphenyl, phenanthryl, and the like.

The term "spiro compound" refers to a chemical compound that exhibits a twisted structure of two or more rings (ring system) in which two or three rings are linked together by one common atom.

The terms "halo" and "halogen" and "halide" are used in the conventional sense to refer to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) substituents. ..

As used herein, the terms "cis" / "Z" and "trans" / "E" are used interchangeably to refer to double bond geometry.

"Hydrocarbyl" refers to a monovalent hydrocarbyl radical containing 1 to 24 carbon atoms, most preferably 1 to 12 carbon atoms, and is a linear, branched, cyclic, saturated and unsaturated species such as. , Alkyl group, alkenyl group, alkynyl group, aryl group and the like. The term "lower hydrocarbyl" refers to a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term "hydrocarbylene" refers to 1 to 24 carbon atoms, preferably Refers to a divalent hydrocarbyl moiety containing 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term "lower hydrocarbylene" refers to a hydrocarbylene group of 1 to 6 carbon atoms. "Substituted hydrocarbyl" refers to hydrocarbyl substituted with one or more substituents, and the terms "heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer to hydrocarbyl in which at least one carbon atom has been replaced with a heteroatom. .. Similarly, "substituted hydrocarbylene" refers to hydrocarbylene substituted with one or more substituents, and the terms "heteroatom-containing hydrocarbylene" and "heterohydrocarbylene" refer to at least one. Refers to hydrocarbylene in which a carbon atom is replaced with a heteroatom. Unless otherwise indicated, the terms "hydrocarbyl" and "hydrocarbylene" should be construed to include substitution and / or heteroatom-containing hydrocarbyl moieties and hydrocarbylene moieties, respectively.

The term "heteroatom-containing" as in "heteroatom-containing hydrocarbyl group" means that one or more carbon atoms are non-carbon atoms such as nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen. , Refers to a hydrocarbon molecule or hydrocarbyl molecule fragment that has replaced oxygen or sulfur. Similarly, the term "heteroalkyl" refers to heteroatom-containing alkyl substituents, and the term "heterocyclic" refers to heteroatom-containing cyclic substituents, "heteroaryl" and "heteroaromatics." The terms "" refer to heteroatom-containing "aryl" and "aromatic" substituents, respectively. The "heterocyclic" group or compound may be aromatic or non-aromatic, and the "heterocyclic substance" is monocyclic, as described above with respect to the term "aryl". Note that it may be bicyclic, or polycyclic. Examples of heteroalkyl groups include, but are not limited to, alkoxyaryls, alkylsulfanil-substituted alkyls, N-alkylated aminoalkyls and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, and examples of heteroatom-containing alicyclic groups include pyrrolidino. , Morphorino, piperazino, piperidino, etc., but are not limited to these.

A "substitution" such as "substituted hydrocarbyl", "substituted alkyl", "substituted aryl", etc., is a carbon (in hydrocarbyl, alkyl, aryl or other moiety) as implied in some of the above definitions. It is intended that at least one hydrogen atom attached to an (or other) atom replaces one or more non-hydrogen substituents. Examples of such substituents are, but are not limited to, halos, hydroxyls, sulfhydryls, C _{1 to} C ₂₄ alkoxy, C _{2 to} C ₂₄ alkenyloxy, C _{2 to} C ₂₄ alkynyloxy, C ₅ to C. ₂₄ aryloxy, C _{6 to} C ₂₄ aralkyloxy, C _{6 to} C ₂₄ alkaline ruoxy, acyl (C _{2 to} C ₂₄ alkylcarbonyl (-CO-alkyl) and C _{6 to} C ₂₄ arylcarbonyl (-CO-aryl)) the included), including acyloxy (-O- _acyl) (C 2 _{-C 24} alkylcarbonyloxy (-O-CO- alkyl) and _C 6 _{-C 24} arylcarbonyloxy (-O-CO- aryl)), C _{2 to} C ₂₄ alkoxycarbonyl (-(CO) -O-alkyl), C _{6 to} C ₂₄ aryloxycarbonyl (-(CO) -O-aryl), halocarbonyl (-CO) -X (in the formula, X is is _halo), C 2 _{-C 24} alkylcarbonyl diisocyanatohexane (-O- (CO) -O- _alkyl), C 6 _{-C 24} aryl carbonium diisocyanatohexane (-O- (CO) -O- aryl), carboxy (- COOH), carbamoyl _{(- (CO) -NH 2)} , mono- _{- (C} 1 _{~C 24} alkyl) -substituted carbamoyl _{(- (CO) -NH (C} 1 ~C 24 alkyl)), di - _(C 1 -C _24- alkyl) substituted carbamoyl (-(CO) -N (C _{1 to} C ₂₄ alkyl) ₂ ), mono- (C _{1 to} C ₂₄ haloalkyl) substituted carbamoyl (-(CO) -NH (C _{1 to} C ₂₄ haloalkyl)) ), Di- (C _{1 to} C ₂₄ haloalkyl) substituted carbamoyl (-(CO) -N (C _{1 to} C ₂₄ haloalkyl) ₂ ), Mono- (C _{5 to} C ₂₄ aryl) substituted carbamoyl (-(CO)- NH-aryl), di- (C _{5 to} C ₂₄ aryl) substituted carbamoyl (-(CO) -N (C _{5 to} C ₂₄ aryl) ₂ ), di-N- (C _{1 to} C ₂₄ alkyl), N- (C _{5 to} C ₂₄ aryl) substituted carbamoyl (-(CO) -N (C _{1 to} C ₂₄ alkyl) (C _{5 to} C ₂₄ aryl), thiocarbamoyl (-(CS) -NH ₂ ), mono- (C) _{1 to} C ₂₄ alkyl) substituted thiocarbamoyl (-(CS) -NH (C _{1 to} C ₂₄ alkyl)), di- (C _{1 to} C ₂₄ alkyl) substituted thiocal Bamoyl (-(CS) -N (C _{1 to} C ₂₄ alkyl) ₂ ), mono- (C _{5 to} C ₂₄ aryl) substituted thiocarbamoyl (-(CS) -NH-aryl), di- (C _{5 to} C) _24- aryl) substituted thiocarbamoyl (-(CS) -N (C _{5 to} C ₂₄ aryl) ₂ ), di-N- (C _{1 to} C ₂₄ alkyl), N- (C _{5 to} C ₂₄ aryl) substituted thiocarbamoyl (-(CS) -N (C _{1 to} C ₂₄ alkyl) (C _{5 to} C ₂₄ aryl), carboamide (-NH- (CO) -NH ₂ ), cyano (-C ≡ N), cyanato (-O- C≡N), thiocyanato (-SC≡N), isocyanate (-NCO), thioisocyanate (-NCS), formyl (-(CO) -H), thioformyl (-(CS) -H), amino ( -NH ₂ ), mono- (C _{1 to} C ₂₄ alkyl) substituted amino (-NH (C _{1 to} C ₂₄ alkyl), di- (C _{1 to} C ₂₄ alkyl) substituted amino ((-N (C ₁ to C)) ₂₄ Alkyl) ₂ ), Mono- (C _{5 to} C ₂₄ Aryl) Substituted Amino (-NH (C _{5 to} C ₂₄ Aryl), Di- (C _{5 to} C ₂₄ Aryl) Substituted Amino (-N (C ₅ to C)) _{24 aryl) 2),} C 2 _{-C 24} alkylamido (-NH- (CO) - _alkyl), C 6 _{-C 24} aryl amide (-NH- (CO) - aryl), imino (-CRNH (wherein, R includes H, C _{1 to} C ₂₄ alkyl, C _{5 to} C ₂₄ aryl, C _{6 to} C ₂₄ alkalil, C _{6 to} C ₂₄ aralkyl, etc.), C _{2 to} C ₂₀ alkyl imino (-CRN (alkyl)). (In the formula, R includes, but is not limited to, H, C _{1 to} C ₂₄ alkyl, C _{5 to} C ₂₄ aryl, C _{6 to} C ₂₄ alkaline, C _{6 to} C ₂₄ aralkyl, etc.), aryl imino. (-CRN (aryl) (in the formula, R is, but is not limited to, H, C _{1 to} C ₂₀ alkyl, C _{5 to} C ₂₄ aryl, C _{6 to} C ₂₄ alkalil, C _{6 to} C ₂₄ aralkyl, etc.) (Including), nitro (-NO ₂ ), nitroso (-NO), sulfo (-SO _2- OH), C _1-2 C ₂₄ alkylsulfanyl (-S-alkyl, also referred to as "alkylthio"), C _5- C _24- arylsulfanyl (-S-aryl, "Ali" Also called Ruchio _"), C 1 _{-C 24} alkylsulfinyl (- (SO) - _alkyl), C 5 _{-C 24} arylsulfinyl (- (SO) - _aryl), C 1 _{-C 24} alkylsulfonyl (-SO ₂ - Alkyl), C _1- C ₂₄ monoalkylaminosulfonyl (-SO ₂ N (H) alkyl), C _1- C ₂₄ dialkyl aminosulfonyl (-SO ₂ N (alkyl) ₂ ), C _5- C ₂₄ aryl sulfonyl (-SO 2 N (alkyl) 2) -SO ₂ aryl), boryl _(-BH 2), borono (-B _(OH) 2), boronate (-B _{(oR) 2} (wherein, R, including alkyl or other hydrocarbyl, limited to Not), phosphono (-P (O) (OH) ₂ ), phospho (-PO ₂ ), phosphino (-PH ₂ ), silyl (-SiR ₃ (where R is H or hydrocarbyl in the formula), and Cyriloxy (-O-silyl); and hydrocarbyl moiety C _1- C ₂₄ alkyl (preferably C _1- C ₁₂ alkyl, more preferably C _1- C ₆ alkyl), C _2- C ₂₄ alkenyl (preferably C) ₂ -C ₁₂ alkenyl, more _preferably, C 2 -C _{6 alkenyl),} C 2 _{-C 24} alkynyl _(preferably, C 2 _{-C 12} alkynyl, more _preferably, C 2 -C ₆ alkynyl), _{C 5} - C _24- aryl (preferably C _5- C ₁₄ aryl), C _6- C ₂₄ alkaline (preferably C _6- C ₁₆ alkaline) and C _6- C ₂₄ aralkyl (preferably C _6- C ₁₆ aralkyl) Can be mentioned.

"Functionalization" as in "functionalized hydrocarbyl", "functionalized alkyl", "functionalized olefin", "functionalized cyclic olefin", etc. means hydrocarbyl, alkyl, olefin, cyclic olefin. Or in other parts, it is intended that at least one H atom attached to a carbon (or other) atom replaces one or more functional groups, such as those described above. The term "functional group" is intended to include any functional molecular species suitable for use as described herein. In particular, as used herein, a functional group necessarily has the ability to react with or bind to the corresponding functional group on the surface of the substrate.

In addition, the functional groups described above may be at one or more additional substituents, or at one or more hydrocarbyl moieties (such as those specifically listed above), where specific groups are acceptable. , Further substituted. Similarly, the hydrocarbyl moieties described above may be further substituted with one or more functional groups or additional hydrocarbyl moieties, such as those specifically described above. Similarly, the hydrocarbyl moieties described above may be further substituted with one or more functional groups or additional hydrocarbyl moieties, such as those specifically described above.

"Arbitrary" or "arbitrarily" means that the situation described thereafter may or may not occur, so that description indicates the case in which the situation occurs and the situation in which the situation does not occur. Including cases. For example, the phrase "arbitrarily substituted" means that the non-hydrogen substituent may or may not be present on a given atom, so this description is non-hydrogen. It includes a structure in which a substituent is present and a structure in which a non-hydrogen substituent is absent.

As used herein, the term "terminal olefin" means an olefin, and one of the olefin carbons (ie, the carbon of the carbon-carbon double bond) is at least one non-hydrogen substituent. Substituted by, the other olefin carbons are unsubstituted.

As used herein, the term "zero" means absent or nonexistent.

As used herein, the term "sulfhydryl" represents the basis of the formula "-SH".

As used herein, the term "hydroxyl" represents a group of formula "-OH".

As used herein, the term "carbonyl" represents a group of formula "-C (O)-".

As used herein, the term "ketone" refers to an organic compound having a carbonyl group attached to a carbon atom, such as ^{-C (O) R x , where R x} is as defined above. It can be alkyl, aryl, cycloalkyl, cycloalkenyl, or heterocyclic.

As used herein, the term "ester" refers to an organic compound having a carbonyl group attached to a carbon atom, such as ^{-C (O) OR x , where R x} is as defined above. It can be alkyl, aryl, cycloalkyl, cycloalkenyl, or heterocyclic.

As used herein, the term "amine" ^{represents a group of the formula "-NR x} R ^y ", in which R ^x and R ^y are the same, as defined above. Alternatively, it can be H, alkyl, aryl, cycloalkyl, cycloalkenyl, or heterocycle independently.

As used herein, the term "carboxyl" represents a group of formula "-C (O) O-".

As used herein, the term "sulfonyl" represents a group of _{formula "-SO 2-".}

As used herein, the term "sulfate" represents the basis of _{the formula "-OS (O) 2-O-".}

As used herein, the term "sulfonate" represents the basis of _{the formula "-S (O) 2-O-".}

As used herein, the term "carboxylic acid" represents a group of formula "-C (O) OH".

As used herein, the term "nitro" represents a group of _{formula "-NO 2".}

As used herein, the term "cyano" represents a group of formula "-CN".

As used herein, the term "amide" ^{represents the group of the formula "-C (O) NR x} R ^y ", in which R ^x and R ^y are the same, as defined above. Or independently can be H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle.

As used herein, the term "sulfonamide" _{represents the group of the formula "-S (O) 2} NR ^x R ^y ", in which R ^x and R ^y are as defined above. , The same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle.

As used herein, the term "sulfoxide" represents a group of formula "-S (O)-".

As used herein, the term "phosphonic acid" represents a group of _{formula "-P (O) (OH) 2".}

As used herein, the term "phosphoric acid" represents the group of _{the formula "-OP (O) (OH) 2".}

As used herein, the term "sulfonic acid" represents a group of _{formula "-S (O) 2 OH".}

The formula "H", as used herein, represents a hydrogen atom.

The formula "O", as used herein, represents an oxygen atom.

The formula "N", as used herein, represents a nitrogen atom.

The formula "S", as used herein, represents a sulfur atom.

If the functional group interferes with the metathesis catalyst, the functional group can be protected and any of the protecting groups commonly used in the art can be used. Acceptable protecting groups are described, for example, in Greene et al. , Protective Groups in Organic Synthesis, 5th Ed. It can be found in (New York: Wiley, 2014). Examples of the protecting group include acetal, cyclic acetal, boronate ester (boronate), cyclic boronate ester (cyclic boronate), carbonate and the like. Protecting groups include cyclic acetals or cyclic boronate esters.

Overview Olefin metathesis is a convergence method for constructing CC double bonds in the synthesis of natural products. [Cheng-Sanchez, I. et al. Sarabia, F. et al. Recent Advances in Total Synthesis via Metathesis Reactions. Synthesis 2018, 50, 3749-3786. Furstner, A. et al. Metathesis in Total Synthesis. Chem. Commun. 2011, 47, 6505. Nicolaou, K. Nicola C. Bulker, P. et al. G. Sarlah, D.M. Metathesis Reactions in Total Synthesis. Angew. Chem. Int. Ed. 2005,44,4490-4527. However, it has hardly been applied to the previous synthesis of ^{the Δ 12-PGJ group.} Most importantly, conventional metathesis catalysts have typically resulted in incomplete control of alkene geometry.

Previous synthesis relied on semi-hydrogenation of the alkyne or Witich reaction and required manipulation of multi-step functional groups by concomitant waste formation. From a strategic point of view, chemical selectivity between multiple alkenes was also another concern, especially at a later stage. Stereoselective and alkene chemoselective metathesis catalysts are sought to achieve convergent synthesis from simple alkene construction blocks.

A series of cyclometallated ruthenium-based catalysts (eg, Ru-1, Ru-2) as shown in FIG. 2 have recently been developed by Grubbs and co-workers.

［Ｅｎｄｏ，Ｋ．；Ｇｒｕｂｂｓ，Ｒ．Ｈ．Ｃｈｅｌａｔｅｄ Ｒｕｔｈｅｎｉｕｍ Ｃａｔａｌｙｓｔｓ ｆｏｒ Ｚ−Ｓｅｌｅｃｔｉｖｅ Ｏｌｅｆｉｎ Ｍｅｔａｔｈｅｓｉｓ．Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．２０１１，１３３，８５２５−８５２７．Ｋｅｉｔｚ，Ｂ．Ｋ．；Ｅｎｄｏ，Ｋ．；Ｐａｔｅｌ，Ｐ．Ｒ．；Ｈｅｒｂｅｒｔ，Ｍ．Ｂ．；Ｇｒｕｂｂｓ，Ｒ．Ｈ．Ｉｍｐｒｏｖｅｄ Ｒｕｔｈｅｎｉｕｍ Ｃａｔａｌｙｓｔｓ ｆｏｒ Ｚ−Ｓｅｌｅｃｔｉｖｅ Ｏｌｅｆｉｎ Ｍｅｔａｔｈｅｓｉｓ．Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．２０１２，１３４，６９３−６９９．］ The ruthenium catalyst of FIG. 2 enabled Z-selective metathesis via the preferred syn-metallacyclobutane intermediate (Scheme 1, Path A).

[Endo, K.K. Grubbs, R. et al. H. Selected Ruthenium Catalysts for Z-Selective Olefin Metathesis. J. Am. Chem. Soc. 2011, 133, 8525-8527. Keitz, B.I. K. Endo, K. et al. Patel, P. et al. R. Herbert, M. et al. B. Grubbs, R. et al. H. Applied Ruthenium Catalysis for Z-Selective Olefin Metathesis. J. Am. Chem. Soc. 2012,134,693-699. ]

More recently, the cateco dithiolate catalyst Ru-3 and its dithiolate variants have been developed by the Hoveyda group and have shown high Z selectivity in ring-opening metathesis polymerization, ring-opening cross metathesis, and cross metathesis with Z olefins.

In fact, high kinetic E-selectivity with E-initiating material also defined these catalysts as steric-retaining, Materia Inc. It was also observed using Ru-3, the s-IPr analog Ru-4, and other less bulky fast-starting analogs developed by the Grubbs group. [Johns, A. M. Ahmed, T.M. S. Jackson, B. et al. W. Grubbs, R. et al. H. Pederson, R. et al. L. High Trans Kinetic Selection in Ruthenium-Based Olefin Cross-Metathesis through Stagetion. Org. Lett. 2016, 18, 772-775. Ahmed, T.M. S. Grubbs, R. et al. H. Fast-Initiating, Ruthenium-Based Catalysis for Implemented Activity in Highly E-Selective Cross Metathesis. J. Am. Chem. Soc. 2017,139,1532-1537. Kan, R.M. K. M. Torker, S.A. Hoveyda, A. et al. H. Ready Accessible and Easy Modifice Ru-Based Catalysis for Effective and Z-Selective Ring-Opening Metathesis Polymerization and Ring-Opening. J. Am. Chem. Soc. 2013, 135, 10258-10261. Haveyda, A.M. H. Evolution of Catalytic Stereoselective Olefin Metathesis: From Ancillary Transformation to Stereochemical Identity. J. Org. Chem. 2014,79,4763-4792. Koh, M.M. J. Kan, R.M. K. M. Torker, S.A. Hoveyda, A. et al. H. Broadly Applicable Z-and Diastereoselective Ring-Opening / Cross-Metathesis Catalyzed by a Desiolate Ru Complex. Angew. Chem. Int. Ed. 2014, 53, 1968-1972. ]

The origin of steric retention is due to the formation of side-bound metallocyclobutane intermediates, in which the α-substituents are suppressed to minimize steric interaction with the bulky N-aryl groups of NHC. As a result, starting from the Z alkene, the β-substituted group points downwards to produce a Z alkene product (Scheme 1, Path B). However, starting from the E-alkene, the β-substituted group must point upwards in the open space between the two N-aryl groups and of the E-alkene product (although it has a slower rate). Brings generation (Scheme 1, Path C).

However, cross-metathesis between the two terminal alkenes is not possible with stereoretentive metathesis catalysts because the intermediate methylidene species are unstable and lead to catalytic metathesis. [Koh, M.M. J. Kan, R.M. K. M. Torker, S.A. Yu, M.M. Mikus, M. et al. S. Hoveyda, A. et al. H. High-Value Alcohols and Higher-Oxidation-State Compounds by Catalytic Z-Selective Cross-Metathesis. Nature 2015, 517, 181-186. ]

The methylene capping strategy has recently been reported as a remedy for this problem, allowing cross-metathesis of two terminal alkenes. [Xu, C.I. Shen, X. et al. Hoveyda, A. et al. H. In Situ Methylene Capping: A General Strategy for Effective Catalytic Olefin Metathesis. The Concept, Methodological Applications, and Applications to Synthesis of Biologically Active Compounds. J. Am. Chem. Soc. 2017,139,10919-10928. ] Despite the unique properties of these conformational catalysts, limited synthetic evaluations of these catalysts have been performed to date. [Metathesis metathesis using Ru: Montgomery, T. et al. P. Ahmed, T.M. S. Grubbs, R. et al. H. Stereoretentive Olefin Metathesis: An Avenue to Kinetic Selection. Angew. Chem. Int. Ed. 2017,56,11024-1136. Ahmed, T.M. S. Grubbs, R. et al. H. A Highly Effective Synthesis of Z-Macrocycles P.I. Grubbs, R. et al. H. Using Stereothesis for the Synthesis of E-Macrocycles with Ruthenium-Based Olefin Metathesis Catalysis. Chem. Sci. 2018, 9, 3580-3583. Jung, K.K. Kim, K.K. Sung, J. et al. -C. Ahmed, T.M. S. Hong, S.M. H. Grubbs, R. et al. H. Choi, T. et al. -L. Towerd Perfect Regiocontrol for β-Selective Cyclopolymerization Using a Ru-Based Olefin Metathesis Catalyst. Macromolecules 2018, 51, 4564-4571. Metathesis metathesis using Mo, W: Couturier, J. Mol. -L. Pilet, C.I. Leconte, M. et al. Basset, J. et al. -M. Weiss, K. et al. A Cyclometalated Aryloxy (Chloro) Neopendylide-Tungsten Complex: A Highly Active and Stereoselective Catalyst for the Metals Angew. Chem. Int. Ed. 1992, 31, 628-631. Lam, J. et al. K. Zhu, C.I. Bukhryakov, V.I. Muller, P. et al. Hoveyda, A. et al. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. R. Synthesis of Assessment of Molybdenum and Tungsten Monoariloxide Halide Alkylides for Z-Selective Cross-Metathesis of Cyclooctene. J. Am. Chem. Soc. 2016, 138, 15774-15783. Nguyen, T. et al. T. Koh, M. et al. J. Shen, X. et al. Romiti, F.I. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. R. Hoveyda, A. et al. H. Kinetically Controlled E-Selective Catalytic Olefin Metathesis. Science 2016,352,569-575. Shen, X.I. Nguyen, T. et al. T. Koh, M. et al. J. Xu, D. Speed, A.I. W. H. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. R. Hoveyda, A. et al. H. Kineticly E-Selective Macrocyclic Ring-Closing Metathesis. Nature 2017, 541,380-385. Koh, M.M. J. Nguyen, T. et al. T. Lam, J. et al. K. Torker, S.A. Hyvr, J. et al. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. Schrock, R. R. Hoveyda, A. et al. H. Molybdenum Chloride Catalysis for Z-Selective Olefin Metathesis Reactions. Nature 2017, 542,80-85. ]

In this specification, the olefin strengthen delta ¹² of Figure 1 ^- prostaglandin J Natural Products total synthesis of (1) to (4), it is presented by performing a simple steric holding metathesis approach. It also sets up a complete test ground to assess the reactivity, chemoselectivity, and functional group compatibility of these newly developed metathesis catalysts.

Δ ¹² -PGJ _{3 (3),} for example, by using a solid holding metathesis can be simplified to the truncated prostaglandin structure 22 (Scheme 2).

A relatively pure and commercially available allyl Grignard reagent, ω chain aldehyde 21, and chiral cyclopentenone (R) -6 can be applied to the synthesis of 22. The O-Boc group of (R) -6 can be used as a traceless stereo inducing group to set the C8 stereocenter. [Noyori, R. Suzuki, M. et al. Prostaglandin Synthesis by THREE-Component Coupling. Angew. Chem. Int. Ed. 1984,23,847-876. Arisetti, N. et al. Reiser, O.D. Traceless Stageoinduction for the Entiopure Synthesis of Substituted-2-Cyclopentenones. Org. Lett. 2015, 17, 94-97. ]

Following the retrosynthetic analysis of Δ ^12- PGJ ₃ (3), the purpose was to synthesize ^{Δ 12-} _{PGJ 2 (1).} Therefore, chiral cyclopentenone (R) -6 was prepared from furfuryl alcohol in a three-step process involving a kinetic resolution method developed by Reiser and co-workers (Scheme 3). [Ulbrich, K. et al. Creitmeier, P. et al. Vilaivan, T. et al. Reiser, O.D. Enantioselective Synthesis of 4-Heterosubstituted Cyclopentenones. J. Org. Chem. 2013, 78, 4202-4206. ]

The ω chain aldehyde 10 was prepared from hexanal 7 via asymmetric Keck allylation. [Yadav, J. et al. S. Suresh, B.I. Srihari, P. et al. Stereoselective Total Synthesis of the Marine Macrolide Sanclide A: Total Synthesis of the Marine Macrolide Sanclide A. Euro. J. Org. Chem. 2015, 201, 5856-5863. ] TBS protection and ozonolysis are also shown in (Scheme 4).

3 When all the starting material for the component binding is bound by hand, CuBr · Me 2 _S and LiCl promoted the diastereoselective conjugate addition allylmagnesium bromide. The formed enolate was captured by a subsequently added ω-chain aldehyde electrophile and the O-Boc group was removed during the aldol reaction to form the desired cyclopentenone.

Removal with MsCl and DMAP preferred a reasonable yield (45% over 2 steps, scheme 5) as the primary product.

The three-dimensional retention metathesis was then evaluated at 11. Since eleven cannot react with another terminal alkene using a steric retention metathesis catalyst, the symmetric Z-alkene 13 was considered as the binding partner. It can also be made by twelve homodimerizations readily available through conformational metathesis. When 1 mol% of Ru-4 is charged as a catalyst, 98% conversion by applying a dynamic vacuum to remove the by-product, cis-3-hexene (boiling point 66-68 ° C.) from the reaction mixture. The rate can be achieved. Eleven with an additional 5 mol% catalyst Ru-4 was added to the reaction mixture and the alcohol product 14 could be isolated with high Z selectivity (> 99% Z) in 95% yield. This result established the effectiveness of an efficient one-pot conformation homodimerization / cross metathesis strategy for constructing C5 Z-alkenes.

In contrast, the synthesis of PGE2 and PGF2a required large excess amounts of gaseous butene and more complex manipulations in previously reported methylene capping strategies. [Xu, C.I. Shen, X. et al. Hoveyda, A. et al. H. In Situ Methylene Capping: A General Strategy for Effective Catalytic Olefin Metathesis. The Concept, Methodological Applications, and Applications to Synthesis of Biologically Active Compounds. J. Am. Chem. Soc. 2017,139,10919-10928. ] Ray oxidation and deprotection of the 14 TBS groups in the aqueous HF is over the last two steps, a natural product delta ¹² - supplied prostaglandin _J 2 a (1) in 89% yield.

As shown in Scheme 8, the same three-component binding sequence was carried out to give 16 and the ener functionality of the aldehyde 15 was well tolerated in the aldol process.

16 was then subjected to standard one-pot conformation homodimerization / cross metathesis conditions and the alcohol 17 was subjected to excellent yield (93% yield, scheme) with high Z selectivity (> 99% Z). Obtained in 9). The C14 E-alkene, as previously seen, is consistent with the much slower response of the E-alkene to Ru-4. [Johns, A. M. Ahmed, T.M. S. Jackson, B. et al. W. Grubbs, R. et al. H. Pederson, R. et al. L. High Trans Kinetic Selection in Ruthenium-Based Olefin Cross-Metathesis through Stagetion. Org. Lett. 2016, 18, 772-775. Ahmed, T.M. S. Grubbs, R. et al. H. Fast-Initiating, Ruthenium-Based Catalysis for Implemented Activity in Highly E-Selective Cross Metathesis. J. Am. Chem. Soc. 2017,139,1532-1537. ] The enantiopurity of intermediates 16 and 17 was also evaluated. The three-component binding product 16 had a small loss of enantiopurity (88% ee) from (R) -6 (> 99% ee), but metathesis formation without significant erosion of enantiopurity (87% ee). I got a thing 17.

This result proves that the stereoretention metathesis with the catalyst Ru-4 also retained the stereochemistry of the C8 stereocenter. Ray oxidation of 17 gave 15 deoxy-Δ ^12,14 -prostaglandin J ₂ (2) again in 68% yield.

The synthesis of Δ ¹² -prostaglandin J ₃ (3) began with the preparation of the ω chain aldehyde 21. The present inventors have assumed that the Z-alkene in 21 can also be produced from the steric retention metathesis. First, we obtained chiral alcohol 18 via the reported chiral pool method using (R) -epichlorohydrin as a starting material (Scheme 11). [Bai, Y. Shen, X. et al. Li, Y. Dai, M. et al. Total Synthesis of (-)-Spinosyn A via Carbonylactic Macrolaction. J. Am. Chem. Soc. 2016,138,10838-10841. ]

TBS protection of alcohol 18 followed by removal of 1,3-dithiol gave aldehyde 20. High Z selectivity (> 99% Z) and good yield (88%) by 20 conformation metathesis with excess cis-3-hexene using catalyst Ru-4 (4 mol%). The ω chain aldehyde 21 was obtained. The short synthesis of aldehyde 21 demonstrated that a wide range of functional groups, including aldehydes, can be tolerated using stereoretent metathesis catalysts without protecting group manipulation.
Product 22 was then synthesized from (R) -6 through a standard three-component binding sequence (Scheme 12).

Surprisingly, fast ring closure metathesis (RCM) with Ru-4 yields 24 as a by-product (31% yield) with an abnormal 9-membered ring, with the desired alcohol product 23 being 44%. Was obtained only in the yield of.

Alternatively, we have chosen to use the cyclometallation catalyst Ru-2 to avoid alkene-reactive crossovers. This pathway can be easily avoided in FIG. 4, as the tri-substituted metallocyclobutane intermediate is very unfavorable with this cyclometallation catalyst.

[Herbert, M. et al. B. Grubbs, R. et al. H. Z-Selective Cross Metathesis with Ruthenium Catalysis: Synthetic Applications and Mechanical Applications. Angew. Chem. Int. Ed. 2015, 54, 5018-5024. ] The chemoselective cross metathesis of 5-hexene-1-ol (25) having 22 allylic groups
The desired product 23 was supplied in trace amounts of by-product 26 (less than 2%, scheme 14) in good yield (52%). RCM product 24 was not observed under these conditions.

The side reaction of the internal Z-alkene of C17 may be due to the ethylene produced or the residual ruthenium methylidene species in solution. Then, Ray oxidation and deprotection of the TBS group of 23, in the eight linear steps, delta ¹² - to provide prostaglandin _J 3 (3).

Finally, in _{the synthesis of 15d-PGJ 3} (4) (Scheme 16), a metathesis-reactive crossover between the allyl group and 28 C17 Z alkenes can also be expected. Standard conformational metathesis conditions with Ru-4 provided the desired product 29 in 36% yield and by-products 30 and 31.

28, as well as by-products 29 and 30, were obtained using Ru-2 and no improvement in chemoselectivity was observed. Steric bulk OTBS groups may be beneficial to achieve good chemical selectivity, Δ ¹² -PGJ 3 ₍₃₎ as compared to synthesis, 28 has no such steric hindrance. However, 28 RCMs were not observed due to the ring strain of the RCM product. 30 could not be separated from 29, but the mixture was subjected to pyridinium chlorochromate (PCC) oxidation and Pinkick oxidation conditions to 15-deoxy-Δ ^12,14 -prostaglandin J ₃ (4) (from 28). 12% yield) was made possible to isolate. Ray oxidation of the mixture of 29 and 30 was also performed, resulting in a significant amount of degradation products.

In conclusion, the present inventors have found that in the three-dimensional retaining and shorter sequences given capacity by stereoselective metathesis (7-8 steps in the longest linear sequence), four delta ^{12 -} prostaglandin J Natural Products A concise convergent synthesis was achieved. Furthermore, the reactivity, chemoselectivity, and functional group compatibility of steric retention metathesis were evaluated. This study suggests further practical applications of stereoselective metathesis such as easy one-pot stereoretention homodimerization / cross metathesis strategies for introducing Z-alkenes with good geometric control. Should be done. The modularity and convenience of this chemistry opens up the synthesis of other prostaglandins and analogs, enabling SAR studies in the treatment of cancer. In well-defined kinetic Z / E selective catalysts developed to overcome the inherent thermodynamic preferences of alkene product geometry, olefin metathesis plays a vital role in synthetic design. Can be fulfilled.
Olefin metathesis catalyst

［式中、
Ｘは、Ｏ又はＳであり、
Ｙは、Ｏ又はＳであり、
Ｚは、Ｎ又はＣＲ^３２であり、
Ｗは、Ｏ、ハロゲン、ＮＲ^３３又はＳであり、
Ｒ^１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２と共にスピロ化合物を形成してもよく、又はＲ^３と共に若しくはＲ^４と共に、多環式環を形成してもよく、
Ｒ^２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１と共にスピロ化合物を形成してもよく、又はＲ^３と共に若しくはＲ^４と共に、多環式環を形成してもよく、
Ｒ^３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２と共に若しくはＲ^１と共に、多環式環を形成してもよく、又はＲ^４と共にスピロ化合物を形成してもよく、
Ｒ^４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^３と共にスピロ化合物を形成してもよく、又はＲ^２と共に若しくはＲ^１と共に、多環式環を形成してもよく、
Ｒ^５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^６と共に、任意に置換された多環式環を形成してもよく、
Ｒ^６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^５と共に若しくはＲ^７と共に、任意に置換された多環式環を形成してもよく、
Ｒ^７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^６と共に若しくはＲ^８と共に、任意に置換された多環式環を形成してもよく、
Ｒ^８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^７と共に若しくはＲ^９と共に、任意に置換された多環式環を形成してもよく、
Ｒ^９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^８と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１１と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１０と共に若しくはＲ^１２と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１１と共に若しくはＲ^１３と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１４と共に若しくはＲ^１２と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１３と共に、多環式環を形成してもよく、
Ｒ^１５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１６と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１５と共に若しくはＲ^１７と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１８と共に若しくはＲ^１６と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１７と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、−Ｃ（Ｒ^３４）（Ｒ^３５）ＣＯＯＲ^３６、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）Ｈ、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）Ｒ^３７、−Ｃ（Ｒ^３４）（Ｒ^３５）ＣＲ^３８（ＯＲ^３９）（ＯＲ^４０）、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）ＮＲ^４１Ｒ^４２、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）ＮＲ^４１ＯＲ^４０、−Ｃ（Ｏ）Ｒ^２５、任意に置換された複素環であり、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニル、又はＲ^３３と共に、任意に置換された複素環を形成してもよく、又はＷがハロゲンである場合にはゼロであり、
Ｒ^２０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２１と共に、多環式環を形成してもよく、
Ｒ^２１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２０と共に若しくはＲ^２２と共に、多環式環を形成してもよく、
Ｒ^２２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２１と共に若しくはＲ^２３と共に、多環式環を形成してもよく、
Ｒ^２３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２２と共に、多環式環を形成してもよく、
Ｒ^２４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２５は、ＯＨ、ＯＲ^３０、ＮＲ^２７Ｒ^２８、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ＯＲ^２６、−ＮＲ^２７Ｒ^２８、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３０は、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１９と共に、任意に置換された複素環を形成してもよく、
Ｒ^３４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３７は、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
ｘは、１又は２である。 In one embodiment, the invention provides a steric retaining ruthenium olefin metathesis catalyst represented by the structure of formula (I).

[During the ceremony,
X is O or S,
Y is O or S,
Z is N or CR ³²
W is O, halogen, NR ³³ or S.
R ¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 2} , or polycyclic with ^{R 3} or with R ^4. May form a ring,
R ² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 1} , or polycyclic with ^{R 3} or with R ^4. May form a ring,
R ³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ² or with R ¹ may form a polycyclic ring, or with R ⁴ Spiro compounds may be formed
R ⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 3} , or polycyclic with ^{R 2} or with R ^1. May form a ring,
R ⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁶ may form an optionally substituted polycyclic ring.
R ⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together or R ⁷ together with R ^5, may form a polycyclic ring which is optionally substituted,
R ⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ⁶ or with R ^8, may form a polycyclic ring which is optionally substituted,
R ⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ⁷ or with R ^9, may form a polycyclic ring which is optionally substituted,
R ⁹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁸ may form an optionally substituted polycyclic ring.
R ¹⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹¹ may form an optionally substituted polycyclic ring.
R ¹¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ¹⁰ or together with R ^12, may form a polycyclic ring which is optionally substituted,
R ¹² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ¹¹ or together with R ^13, may form a polycyclic ring which is optionally substituted,
R ¹³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ¹⁴ or together with R ^12, may form a polycyclic ring which is optionally substituted,
R ¹⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹³ may form a polycyclic ring.
R ¹⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹⁶ may form an optionally substituted polycyclic ring.
R ¹⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} substituted aryl, or an optionally C _{3 to 8} substituted cycloalkenyl, or together with R ¹⁵ or together with R ^17, may form a polycyclic ring which is optionally substituted ,
R ¹⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} substituted aryl, or an optionally C _{3 to 8} substituted cycloalkenyl, or together with R ¹⁸ or together with R ^16, may form a polycyclic ring which is optionally substituted ,
R ¹⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹⁷ may form an optionally substituted polycyclic ring.
R ¹⁹ is H, optionally substituted C _1-24 alkyl, -C (R ³⁴ ) (R ³⁵ ) COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O) H, -C (R). ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , -C (O) R ²⁵ , optionally substituted heterocycle, optionally substituted C _3-8 cyclo Arbitrarily substituted heterocycles may be formed with alkyl, optionally substituted C _{5 to 24} aryl, optionally substituted C _{3 to 8} cycloalkenyl, or R ³³ , or W is a halogen. If it is zero,
R ²⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ may form a polycyclic ring.
R ²¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²⁰ or with R ²² may form a polycyclic ring.
R ²² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ or with R ²³ may form a polycyclic ring.
R ²³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²² may form a polycyclic ring.
R ²⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl.
R ²⁵ was OH, OR ³⁰ , NR ²⁷ R ²⁸ , optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted. C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl,
R ²⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁷ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁹ is H, optionally substituted C _{1 to 24} alkyl, OR ²⁶ , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted. C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl.
R ³⁰ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally substituted. C _3-8 cycloalkenyl,
R ³¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³³ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. C _3-8 cycloalkenyl substituted with, or with R ¹⁹ may form an optionally substituted heterocycle.
R ³⁴ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁵ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁷ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally substituted. C _3-8 cycloalkenyl,
R ³⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴⁰ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
x is 1 or 2.

Substituents where specific groups such as C _{1 to 24} alkyl, C _{3 to 8} cycloalkyl, heterocycles, C _{5 to 24} aryl, C _{3 to 8} cycloalkenyl groups, or polycyclic rings are optionally substituted. Halogen, -OH, -SH, C _{1 to} C ₂₄ alkoxy, C _{2 to} C ₂₄ alkenyloxy, C _{2 to} C ₂₄ alkynyloxy, C _{5 to} C ₂₄ aryloxy, C _{6 to} C ₂₄ aralkyloxy, C. _{6 to} C ₂₄ Alkaline Luoxy, -CO- (C _{1 to} C ₂₄ Alkyl), -CO- (C _{6 to} C ₂₄ Aryl), -O-CO- (C _{1 to} C ₂₄ Alkyl), -O-CO -(C _{6 to} C ₂₄ aryl),-(CO) -O- (C _{1 to} C ₂₄ alkyl),-(CO) -O- (C _{6 to} C ₂₄ aryl), (-O- (CO)- O- (C _{1 to} C ₂₄ alkyl), -O- (CO) -O- (C _{6 to} C ₂₄ aryl), (-COOH), (-(CO) -NH ₂ ), (-(CO)- NH (C _{1 to} C ₂₄ alkyl)), (-(CO) -N (C _{1 to} C ₂₄ alkyl) ₂ ),-(CO) -NH- (C _{6 to} C ₂₄ aryl), (-(CO) -N (C _{5 to} C ₂₄ aryl) ₂ ), (-(CO) -N (C _{1 to} C ₂₄ alkyl) (C _{5 to} C ₂₄ aryl), (-(CS) -NH ₂ ), (-( CS) -NH (C _{1 to} C ₂₄ alkyl)), (-(CS) -N (C _{1 to} C ₂₄ alkyl) ₂ ),-(CS) -NH- (C _{6 to} C ₂₄ aryl), (-) (CS) -N (C _{5 to} C ₂₄ aryl) ₂ ), di-N- (C _{1 to} C ₂₄ alkyl), (-(CS) -N (C _{1 to} C ₂₄ alkyl) (C _{5 to} C ₂₄₎ Aryl), (-NH- (CO) -NH ₂ ), (-C≡N), (-O-C≡N), (-S-C≡N), (-NCO), (-NCS), (-(CO) -H), (-(CS) -H), (-NH ₂ ), (-NH (C _{1 to} C ₂₄ alkyl), ((-N (C _{1 to} C ₂₄ alkyl) ₂ )) , (-NH (C _{5 to} C ₂₄ aryl), (-N (C _{5 to} C ₂₄ aryl) ₂ ), -NH- (CO)-(C _{1 to} C ₆ alkyl), -NH- (CO)- (C _{6 to} C ₂₄ aryl), -C (C _{1 to} C ₂₄ alkyl) (NH), (-CHN (C _{1 to} C ₂₄ alkyl) , (-CHN (C _{6 to} C ₂₄ aryl), (-NO ₂ ), (-NO), (-SO _2- OH), -S- (C _{1 to} C ₂₄ alkyl), (-S- (C) _{5 to} C ₂₄ aryl), (-(SO)-(C _{1 to} C ₂₄ alkyl), (-(SO)-(C _{5 to} C ₂₄ aryl), SO _2- (C _{1 to} C ₂₄ alkyl), ( -SO _2- N (H) (C _{1 to} C ₂₄ alkyl), (-SO _2- N (C _{1 to} C ₂₄ alkyl) ₂ ), (-SO _2- (C _{5 to} C ₂₄ aryl), (-SO 2-N (H) (C 1 to C 24 aryl)) BH ₂ ), B (OH) ₂ ), (-B (O) (C _{1 to} C ₂₄ alkyl) ₂ , (-P (O) (OH) ₂ ), (-PO ₂ ), (-PH ₂ ) , -SiH ₃ , (-O-silyl), C _{1 to} C ₂₄ alkyl, C _{1 to} C ₁₂ alkyl, C _{1 to} C ₆ alkyl, C _{2 to} C ₂₄ alkenyl, C _{2 to} C ₁₂ alkenyl, C ₂ to C ₆ alkenyl, C _{2 to} C ₂₄ alkynyl, C _{2 to} C ₁₂ alkynyl, C _{2 to} C ₆ alkynyl, C _{5 to} C ₂₄ aryl, C _{5 to} C ₁₄ aryl, C _{6 to} C ₂₄ alkaline, C _{6 to} C ₁₆ alkaline, C _{6 to} C ₂₄ aralkyl, and C _{6 to} C ₁₆ aralkyl, as defined herein.

In another embodiment, the invention provides a catalyst represented by formula (I), where X is S, Y is S, Z is N or CR ³² , and W is. , O, NR ³³ , or S, R ¹ is H, optionally substituted C _1-12 alkyl, halogen, R ² is H, optionally substituted C _1-12 alkyl, halogen. R ³ is H, optionally substituted C _1-12 alkyl, halogen, R ⁴ is H, optionally substituted C _1-12 alkyl, halogen, R ⁵ is H. , Arbitrarily substituted C _1-12 alkyl, halogen, R ⁶ is H, optionally substituted C _1-12 alkyl, halogen, R ⁷ is H, optionally substituted C _{1 ~ 12} alkyl, halogen, R ⁸ is H, optionally substituted C _1-12 alkyl, halogen, R ⁹ is H, optionally substituted C _1-12 alkyl, halogen. R ¹⁰ is H, optionally substituted C _1-12 alkyl, halogen, R ¹¹ is H, optionally substituted C _1-12 alkyl, halogen, R ¹² is H, optionally Substituted C _1-12 alkyl, halogen, R ¹³ is H, optionally substituted C _1-12 alkyl, halogen, R ¹⁴ is H, optionally substituted C _1-12 alkyl. , Haloalkane, R ¹⁵ is H, optionally substituted C _1-12 alkyl, halogen, optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C. _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, R ¹⁶ is H, optionally substituted C _{1 to 12} alkyl, halogen, optionally substituted heterocycle, optionally. Substituted C _3-8 cycloalkyl, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, R ¹⁷ is H, optionally substituted C _{1 ~ 12} alkyl, halogen, optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C _6-10 aryl, optionally substituted C _3-8 cycloalkenyl. or together with R ^18, may form a polycyclic ring, R ¹⁸ is substituted H, optionally substituted C _{1 to 12} alkyl, halogen, optionally substituted heterocycle, optionally C _3-8 cycloalkyl, optionally substituted C _6-10 aryls, optionally substituted C _3-8 cycloalkenyl, or may form a heterocyclic ring with ^{R 17 , where R 19} is H, optionally substituted. C _1-12 Alkyl, -C (R ³⁴ ) (R ³⁵ ) -COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) -C (O) H, -C (R ³⁴ ) (R ³⁵ ) -C ( O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) -CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) -C (O) -NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) -C (O) -NR ⁴¹ OR ⁴⁰ , -C (O) R ²⁵ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional Arbitrarily substituted heterocycles may be formed with C _6-10 aryl substituted with, optionally substituted C _3-8 cycloalkenyl, or R ^{33 , where R 20} is H, optionally substituted. C _1-12 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) ) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C _6-10 aryl either a _{C 3 to 8} cycloalkenyl optionally substituted, or together with ^{R 21,} may form a polycyclic ^{ring, R 21} is, H, _{C 1 to 12} alkyl optionally substituted, halogen , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C _6-10 aryl, optionally substituted C _3-8 cycloalkenyl. Or with R ²⁰ or with R ²² , a polycyclic ring may be formed, where R ²² is H, optionally substituted C _1-12 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C _6-10 aryl, optionally substituted C _3-8 cycloalkenyl, or R Young with ²¹ The properly with R ^23, may form a polycyclic ring, R ²³ is, H, optionally substituted C _{1 to 12} alkyl, halogen, optionally substituted heterocycle, C optionally substituted _3-8 cycloalkyl, optionally substituted C _6-10 aryl, optionally substituted C _3-8 cycloalkenyl, or with R ²² may form a heterocyclic ring, R ^24. Is H, R ²⁵ is OH, OR ³⁰ , NR ²⁷ R ²⁸ , optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, Arbitrarily substituted C _6-10 aryl, or optionally substituted C _3-8 cycloalkenyl, R ²⁶ is H, optionally substituted C _1-12 alkyl, optionally substituted C _{3 ~ 8} Cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, or optionally substituted C _3-8 cycloalkenyl, where R ²⁷ is H, optionally substituted. With C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, or optionally substituted C _3-8 cycloalkenyl. Yes, R ²⁸ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, Or optionally substituted C _3-8 cycloalkenyl, R ²⁹ is H, optionally substituted C _1-12 alkyl, OR ²⁶ , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optional. C _3-8 cycloalkyl substituted with, optionally substituted C _6-10 aryl, or optionally substituted C _3-8 cycloalkenyl, where R ³⁰ is optionally substituted C _1-12. Alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, or optionally substituted C _3-8 cycloalkenyl, R ^31. Is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, or optionally substituted. C _3-8 cycloalkenyl, R ³² is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloal. Kill, optionally substituted heterocycle, optionally substituted C _6-10aryl , or optionally substituted C _3-8 cycloalkenyl, R ³³ is H, optionally substituted C _{1 to 12} alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, optionally substituted C _3-8 cycloalkenyl, or Arbitrarily substituted heterocycles may be formed with R ^{19 , where R 34} is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted. Heterocycles, optionally substituted C _6-10aryl , or optionally substituted C _3-8 cycloalkenyl, R ³⁵ is H, optionally substituted C _1-12 alkyl, optionally. Substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10aryl , or optionally substituted C _3-8 cycloalkenyl, where R ³⁶ is H, Arbitrarily substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, or optionally substituted C _{3 ~ 8} Cycloalkenyl, R ³⁷ is optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 ~ 10} aryl, or optionally substituted C _3-8 cycloalkenyl, where R ³⁸ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted. Heterocycles, optionally substituted C _6-10aryl , or optionally substituted C _3-8 cycloalkenyl, R ³⁹ is H, optionally substituted C _1-12 alkyl, optionally. substituted _{C 3 to 8} cycloalkyl, optionally substituted heterocycle, _{C 6 to 10} aryl, or an optionally substituted _{C 3 to 8} cycloalkenyl optionally ^{substituted, R 40} is, H, Arbitrarily substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, or optionally substituted C _{3 ~ 8} Cycloalkenyl, R ⁴¹ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted. Heterocycle, optionally substituted C _6-10 aryl, or optionally substituted C _3-8 cycloalkenyl, where R ⁴² is H, optionally substituted C _1-12 alkyl, optionally substituted. C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _6-10 aryl, or optionally substituted C
_{It is 3 to 8} cycloalkenyl, and x is 1 or 2.

In another embodiment, the invention provides a catalyst represented by formula (I), where X is S, Y is S, Z is N or CR ³² , and W is. , O or NR ³³ , R ¹ is H, straight chain or branched chain C _1-6 alkyl, or halogen, and R ² is H, straight chain or branched chain C _1-6 alkyl, or halogen. Hhalo, R ³ is H, linear or branched C _1-6 alkyl, or halogen, R ⁴ is H, linear or branched C _1-6 alkyl, or halogen. R ⁵ is H, linear or branched C _{1 to 6} alkyl, R ⁶ is H, linear or branched C _{1 to 6} alkyl, and R ⁷ is H, linear or branched. a Edakusari _{C 1 to 6} alkyl, ^{R 8} is H or _{C 1 to 6} alkyl, ^{R 9} is H, a linear or branched _{C 1 to 6} ^{alkyl, R 10} is H, Straight chain or branched chain C _1-6 alkyl, R ¹¹ is H, straight chain or branched chain C _1-6 alkyl, R ¹² is H, straight chain or branched chain C _1-6 ^{alkyl, R 13} is, H, or a linear or branched _{C 1 to 6} alkyl, or a naphthyl ring is formed together with ^{R 14, R 14} is, H, linear or branched _{C. 1 to 6} alkyl or form a naphthyl ring with ^{R 13 , R 15} forms a naphthyl ring with H, phenyl, linear or branched C _1-6 alkyl, halogen, or R ¹⁶ and R ¹⁶ Form a naphthyl ring with H, phenyl, linear or branched chain C _1-6 alkyl, halogen, or R ¹⁵ or with R ^{17 , where R 17} is H, phenyl, linear or branched chain C. ₆ alkyl, halogen, or together with ^{R 16,} or a naphthyl ring is formed together with ^{R 18, R 18} is, H, phenyl, straight-chain or branched-chain _{C 1-6} alkyl, halogen, or together with ^{R 16,} or Forming a naphthyl ring with R ^{18 , R 19} is H, phenyl, C _1-6 alkyl, -C (R ³⁴ ) (R ³⁵ ) COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O). H, -C (R ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , forming a 5, 6 or 7-membered heterocycle with R ^33. R ²⁰ is H, linear or branched chain C _1-16 alkyl, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S. (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) _2, -SR ³¹ , pyridine, piperidine, imidazole, indridin, indazole, optionally substituted C _{3 to 8} Cycloalkyl, phenyl, naphthalene, cyclohexene, or R ²¹ may form a polycycle, where R ²¹ is H, phenyl, -NR ²⁷ R ²⁸ , linear or branched C _1-6 alkyl, Polycycles may be formed with halogen, or with R ²⁰ or with R ^{22 , where R 22} is H, linear or branched C _1-6 alkyl, halogen, -C (O) R ²⁵ , -OR. ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) _2, -SR ³¹ , pyridine, piperidine, imidazole, indolizine, indazole, _{C 3 to 8} cycloalkyl optionally substituted, phenyl, naphthalene, cyclohexene, or together with ^{R 21,} or together with ^{R 23,} may form a ^{polycyclic, R 23} Is H, phenyl, linear or branched C _1-6 alkyl, or can form a polycycle with ^{R 22 and R 24} is H, linear or branched C _1-6. Alkyl, R ²⁵ is OH, OR ³⁰ , NR ²⁷ R ²⁸ , linear or branched C _{1 to 6} alkyl, R ²⁶ is H, linear or branched C _{1 to 6} alkyl. Yes, R ²⁷ is H, straight chain or branched chain C _1-6 alkyl, R ²⁸ is H, straight chain or branched chain C _1-6 alkyl, and R ²⁹ is H, straight chain. Alternatively, the branch chain C _1-6 alkyl, −NR ²⁷ R ²⁸ −, where R ³⁰ is optionally substituted C _1-6 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted. Heterocyclic, optionally substituted phenyl, or optionally substituted C _3-8 cycloalkenyl, R ³¹ is H, linear or branched C _{1 to 6} alkyl, and R ³² is. H, straight chain or branched chain C _1-6 alkyl, R ³³ is H, straight chain or branched chain C _1-6 alkyl, or with R ¹⁹ , 5 member, 6 member, or 7 member Form a heterocycle, R ³⁴ is H, or straight chain or branched chain C _1-6 alkyl, R ³⁵ is H, or straight chain or branched chain C _1-6 alkyl, and R ³⁶ is H, straight chain or branched chain C 1-6 alkyl. Branched chain C _1-6 alkyl, R ³⁷ is straight chain or branched chain C _1-6 alkyl, R ³⁸ is H, or straight chain or branched chain C _1-6 alkyl. R ³⁹ is H, straight chain or branched chain C _1-6 alkyl, R ⁴⁰ is H, straight chain or branched chain C _1-6 alkyl, R ⁴¹ is H, straight chain or branched chain. a Edakusari _{C 1 to 6} ^{alkyl, R 42} is, H, a linear or branched _{C 1 to 6} alkyl, x is 1 or 2.

In one embodiment, the present invention provides a catalyst represented by formula (I), in which X is S, Y is S, Z is N or CR ³² , and W is. O, NR ³³ , or S, R ¹ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or H, and R ² is Me, Et. , i-Pr, n-Pr , n-Bu, t-Bu, s-Bu, or a H, ^{R 3} is, H, Me, Et, i -Pr, n-Pr, n-Bu, t- Bu or s-Bu, R ⁴ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ⁵ is H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ⁶ is H, F, Cl, Br, I, Me, Et. , I-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, where R ⁷ is H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, an n-Bu, t-Bu, or s-Bu, ^{R 8} is, H, F, Cl, Br , I, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, R ⁹ is H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ¹⁰ is , H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ¹¹ is H, Me, F, Cl, Br, I, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, where R ¹² is H, F, Cl, Br, I, Me, Et, i-Pr. a n-Pr, n-Bu, t-Bu, or ^{s-Bu, R 13} is, H, Me, F, Cl , Br, I, Et, n-Pr, i-Pr, n-Bu, a t-Bu, or ^{s-Bu, R 14} is, F, Cl, Br, I , Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or H Yes, R ¹⁵ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, F, Br, I, Cl, or naphthyl or phenanthryl with ^{R 16 Is R 16} forming a ring and R 16 is H, F, Cl, Br, I, or is R ¹⁵ forming a naphthyl or phenanthryl ring and R ¹⁷ being H, F, Cl, Br, I? or naphthyl or phenanthryl forms a ring together with ^{R 18, R 18} is, H, Cl, F, Br , I, 3,5- di Chloro-phenyl, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or form naphthyl or phenanthryl with ^{R 17 , where R 19} is H, _phenyl, C 1 _{~ 6} ^{alkyl, -C (R 34) (R} 35) COOR 36, -C (R 34) (R 35) C (O) H, -C (R 34) (R 35) C (O ) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , where R ²⁰ is H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s. -Bu, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ ,- OP (O) (OH) ₂ , -SR ³¹ , pyridine, piperidine, imidazole, indridin, indazole, optionally substituted C _3-8 cycloalkyl, phenyl, naphthalene, or cyclohexene, where R ²¹ is H. , Phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR ²⁷ R ²⁸ F, Cl, Br, or I, where R ²² is H, Me. , Et, i-Pr, ^{halogen, -C (O) R 25,} -OR 26, CN, -NR 27 R 28, NO 2, - CF 3, -S (O) x R 29, -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , pyridine, piperidine, imidazole, indridin, indazole, cyclohexyl, phenyl, naphthalene, cyclohexene F, Cl, Br, or I, R ²² H, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , _{-OP (O) (OH) 2} , or ^{-SR 31} - a ^{and, R 23} is, H, F, Cl, Br , I, phenyl, Me, Et, i-Pr , n-Pr, n-Bu, It is t-Bu or s-Bu, R ²⁴ is H, R ²⁴ is H or Me, and R ²⁵ is OH, OR ³⁰ , NR ²⁷ R ²⁸ , Me, Et. , Or i-Pr, R ²⁶ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ²⁷ is H, Me, Et. , Or i-Pr, R ²⁸ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ²⁹ is H, Me, Et. , I-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or -NR ²⁷ R ²⁸ , where R ³⁰ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu or s-Bu, R ³¹ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ³² is Me, Me, Et, n-Pr, or H, where R ³³ is H, Me, Et, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or R ¹⁹ Together with morpholino, thio-morpholino, pyrrolidino, piperidino, or piperazino ring, R ³⁴ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu. , R ³⁵ is H, or Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ³⁶ is H, Me, Et, i-Pr, n. -Pr, n-Bu, t-Bu, or s-Bu, where R ³⁷ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, R ³⁸ is H or Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ³⁹ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, where R ⁴⁰ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, R ^41. Is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ⁴² is H, Me, Et, i-Pr, n-Pr, n. -Bu, t-Bu, or s-Bu, where x is 1 or 2.

In one embodiment, the present invention provides a catalyst represented by formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is Me or H, R ² is Me or H, R ³ is H, R ⁴ is H, and R ⁵ is H, F, Me, t-Bu, or i-. Pr, R ⁶ is H or t-Bu, R ⁷ is H, F, or Me, R ⁸ is H, F, or t-Bu, and R ⁹ is H, F, Me, t-Bu, or i-Pr, R ¹⁰ is H, F, Me, t-Bu, or i-Pr, R ¹¹ is H or t-Bu, R ¹² Is H, F, or Me, R ¹³ is H, F, or t-Bu, R ¹⁴ is F, Me, i-Pr, t-Bu, or H, and R ¹⁵ is. , H, Me, F, Br, I, or a Cl, or naphthyl is formed together with ^{R 16, R 16} are either H, or naphthyl is formed together with ^{R 15, R 17} is H or naphthyl or phenanthryl forms a ring together with ^{R 18, R 18} are, Cl, F, Br, I, 3,5-dichloro - phenyl, naphthyl or phenanthryl phenyl or a t-Bu, or together with ^{R 17} Forming a ring, R ¹⁹ is i-Pr, R ²⁰ is H or phenyl, R ²¹ is H, and R ²² is H, -C (O) R ²⁵ , -OR ²⁶ , CN. _{^{, -NR 27 R 28, NO 2}} , -CF 3, -S (O) x R 29, -P (O) (OH) 2, -OP (O) (OH) 2, -SR 31 - a and, R ²³ is H, R ²⁴ is H, R ²⁵ is OH, OR ³⁰ , NR ²⁷ R ²⁸ , Me, Et, or i-Pr, and R ²⁶ is H, Me, Et, i. -pr, an n-Pr, n-Bu, t-Bu, or ^{s-Bu, R 27} is, H, Me, Et, i -Pr, n-Pr, n-Bu, t-Bu, or s -Bu, R ²⁸ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ²⁹ is H, Me, Et, i-. Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR ²⁷ R ²⁸ , where R ³⁰ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, Or s-Bu, where R ³¹ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu.

In one embodiment, the invention provides a catalyst represented by formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is Me, R ² is Me, R ³ is H, R ⁴ is H, R ⁵ is F, R ⁶ is H, and R ⁷ is H or F. , R ⁸ is H, R ⁹ is F, R ¹⁰ is F, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is F, and so on. R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is phenyl and R ²¹ is H. , R ²² is H, R ²³ is H, and R ²⁴ is H.

In one embodiment, the invention provides a catalyst represented by formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is Me, R ⁶ is H, R ⁷ is Me, R ⁸ Is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H, R ¹² is Me, R ¹³ is H, R ¹⁴ is Me, and R ¹⁵ is. Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is phenyl, R ²¹ is H, R ²² Is H, R ²³ is H, and R ²⁴ is H.

In one embodiment, the invention provides a catalyst represented by formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, and so on. R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, and R ¹⁴ is i. -Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is phenyl, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

In one embodiment, the invention provides a catalyst represented by formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is Me, R ² is Me, R ³ is H, R ⁴ is H, R ⁵ is F, R ⁶ is H, and R ⁷ is H or F. , R ⁸ is H, R ⁹ is F, R ¹⁰ is F, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is F, and so on. R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, and R ²¹ is H. , R ²² is H, R ²³ is H, and R ²⁴ is H.

In one embodiment, the invention provides a catalyst represented by formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is Me, R ⁶ is H, R ⁷ is Me, R ⁸ Is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H, R ¹² is Me, R ¹³ is H, R ¹⁴ is Me, and R ¹⁵ is. Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² Is H, R ²³ is H, and R ²⁴ is H.

In one embodiment, the invention provides a catalyst represented by formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, and so on. R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, and R ¹⁴ is i. -Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

であり、式中、Ｒ^４３は、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、「ｆ」は０、１、２、３、又は４である。 In one embodiment, the invention provides a compound, part of formula (I).

In the equation, R ⁴³ is optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) xR ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cyclo Alkyl, optionally substituted C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl, where "f" is 0, 1, 2, 3, or 4.

であり、式中、Ｒ^１９、Ｒ^２０、Ｒ^２７、Ｒ^２８、Ｒ^４３、及び「ｆ」は、本明細書に定義されるとおりである。 In one embodiment, the invention provides a compound of formula (I).

In the formula, R ¹⁹ , R ²⁰ , R ²⁷ , R ²⁸ , R ⁴³ , and “f” are as defined herein.

である。 In one embodiment, the invention provides a compound of formula (I).

Is.

から選択される。 In one embodiment, the present invention provides a compound of formula (I), which comprises:

Is selected from.

式中、
Ｗは、Ｏ、ハロゲン、ＮＲ^３３又はＳであり、
Ｘ^１は、水素、ハロゲン化物、硝酸塩、任意に置換されたＣ_１〜Ｃ_２０アルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_１〜Ｃ_２０アルコキシ、任意に置換されたＣ_１〜Ｃ_２０アルキルカルボキシレート、任意に置換されたＣ_５〜Ｃ_２４アリールオキシ、任意に置換されたＣ_２〜Ｃ_２０アルコキシカルボニル、任意に置換されたＣ_６〜Ｃ_２４アリールオキシカルボニル、任意に置換されたＣ_６〜Ｃ_２４アリールカルボキシレート、任意に置換されたＣ_２〜Ｃ_２４アシル、任意に置換されたＣ_２〜Ｃ_２４アシルオキシ、任意に置換されたＣ_１〜Ｃ_２０アルキルスルホナト、任意に置換されたＣ_５〜Ｃ_２４アリールスルホナト、任意に置換されたＣ_１〜Ｃ_２０アルキルスルファニル、任意に置換されたＣ_５〜Ｃ_２４アリールスルファニル、任意に置換されたＣ_１〜Ｃ_２０アルキルスルフィニル、又は任意に置換されたＣ_５〜Ｃ_２４アリールスルフィニル；
Ｒ^１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２と共にスピロ化合物を形成してもよく、又はＲ^３と共に若しくはＲ^４と共に、多環式環を形成してもよく、
Ｒ^２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１と共にスピロ化合物を形成してもよく、又はＲ^３と共に若しくはＲ^４と共に、多環式環を形成してもよく、
Ｒ^３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２と共に若しくはＲ^１と共に、多環式環を形成してもよく、又はＲ^４と共にスピロ化合物を形成してもよく、
Ｒ^４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^３と共にスピロ化合物を形成してもよく、又はＲ^２と共に若しくはＲ^１と共に、多環式環を形成してもよく、
Ｒ^５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^６と共に、任意に置換された多環式環を形成してもよく、
Ｒ^６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^５と共に若しくはＲ^７と共に、任意に置換された多環式環を形成してもよく、
Ｒ^７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^６と共に若しくはＲ^８と共に、任意に置換された多環式環を形成してもよく、
Ｒ^８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^７と共に若しくはＲ^９と共に、任意に置換された多環式環を形成してもよく、
Ｒ^９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^８と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、−Ｃ（Ｒ^３４）（Ｒ^３５）ＣＯＯＲ^３６、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）Ｈ、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）Ｒ^３７、−Ｃ（Ｒ^３４）（Ｒ^３５）ＣＲ^３８（ＯＲ^３９）（ＯＲ^４０）、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）ＮＲ^４１Ｒ^４２、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）ＮＲ^４１ＯＲ^４０、−Ｃ（Ｏ）Ｒ^２５、任意に置換された複素環であり、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニル、又はＲ^３３と共に、任意に置換された複素環を形成してもよく、又はＷがハロゲンである場合にはゼロであり、
Ｒ^２０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２１と共に、多環式環を形成してもよく、
Ｒ^２１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２０と共に若しくはＲ^２２と共に、多環式環を形成してもよく、
Ｒ^２２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２１と共に若しくはＲ^２３と共に、多環式環を形成してもよく、
Ｒ^２３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２２と共に、多環式環を形成してもよく、
Ｒ^２４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２５は、ＯＨ、ＯＲ^３０、ＮＲ^２７Ｒ^２８、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ＯＲ^２６、−ＮＲ^２７Ｒ^２８、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３０は、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１９と共に、任意に置換された複素環を形成してもよく、
Ｒ^３４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３７は、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
ｘは１又は２であり、アダマンチルは、１つ以上のＣ_１〜６アルキル基によって任意に置換され得る。 In one embodiment, the invention provides a Z-selective ruthenium olefin metathesis catalyst represented by the structure of formula (V).

During the ceremony
W is O, halogen, NR ³³ or S.
X ¹ is hydrogen, halide, nitrate, optionally substituted C _{1 to} C ₂₀ alkyl, optionally substituted C _{5 to} C ₂₄ aryl, optionally substituted C _{1 to} C ₂₀ alkoxy, optionally substituted. C _{1 to} C ₂₀ alkyl carboxylates, optionally substituted C _{5 to} C ₂₄ aryloxy, optionally substituted C _{2 to} C ₂₀ alkoxycarbonyl, optionally substituted C _{6 to} C ₂₄ aryloxycarbonyl , Arbitrarily substituted C _{6 to} C ₂₄ arylcarboxylate, optionally substituted C _{2 to} C ₂₄ acyl, optionally substituted C _{2 to} C ₂₄ acyloxy, optionally substituted C _{1 to} C ₂₀ alkyl Alkoxynat, optionally substituted C _{5 to} C ₂₄ aryl sulfonato, optionally substituted C _{1 to} C ₂₀ alkylsulfanyl, optionally substituted C _{5 to} C ₂₄ aryl sulfanyl, optionally substituted C ₁ -C ₂₀ alkylsulfinyl, or optionally substituted _C 5 _{-C 24} arylsulfinyl;
R ¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 2} , or polycyclic with ^{R 3} or with R ^4. May form a ring,
R ² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 1} , or polycyclic with ^{R 3} or with R ^4. May form a ring,
R ³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ² or with R ¹ may form a polycyclic ring, or with R ⁴ Spiro compounds may be formed
R ⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 3} , or polycyclic with ^{R 2} or with R ^1. May form a ring,
R ⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁶ may form an optionally substituted polycyclic ring.
R ⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together or R ⁷ together with R ^5, may form a polycyclic ring which is optionally substituted,
R ⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ⁶ or with R ^8, may form a polycyclic ring which is optionally substituted,
R ⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ⁷ or with R ^9, may form a polycyclic ring which is optionally substituted,
R ⁹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁸ may form an optionally substituted polycyclic ring.
R ¹⁹ is H, optionally substituted C _1-24 alkyl, -C (R ³⁴ ) (R ³⁵ ) COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O) H, -C (R). ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , -C (O) R ²⁵ , optionally substituted heterocycle, optionally substituted C _3-8 cyclo Arbitrarily substituted heterocycles may be formed with alkyl, optionally substituted C _{5 to 24} aryl, optionally substituted C _{3 to 8} cycloalkenyl, or R ³³ , or W is a halogen. If it is zero,
R ²⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ may form a polycyclic ring.
R ²¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²⁰ or with R ²² may form a polycyclic ring.
R ²² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ or with R ²³ may form a polycyclic ring.
R ²³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²² may form a polycyclic ring.
R ²⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl.
R ²⁵ was OH, OR ³⁰ , NR ²⁷ R ²⁸ , optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted. C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl,
R ²⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁷ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁹ is H, optionally substituted C _{1 to 24} alkyl, OR ²⁶ , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted. C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl.
R ³⁰ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally substituted. C _3-8 cycloalkenyl,
R ³¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³³ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. C _3-8 cycloalkenyl substituted with, or with R ¹⁹ may form an optionally substituted heterocycle.
R ³⁴ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁵ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁷ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally substituted. C _3-8 cycloalkenyl,
R ³⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴⁰ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
x is 1 or 2, and adamantyl can be optionally substituted with _{one or more C 1-6 alkyl groups.}

In one embodiment, the present invention provides a conformational ruthenium olefin metathesis catalyst represented by the structure of formula (V), where W is O and X ¹ is benzoate, pivalate, C ₂ to C. _{6 acyl,} a C 2 -C _{6 alkoxycarbonyl,} C 1 -C ₆ alkyl, _phenoxy, C 1 -C _{6 alkoxy,} C 1 -C ₆ alkylsulfanyl, aryl, or _C 1 -C ₆ alkylsulfonyl, ^{R 1} Is H, optionally substituted C _1-12 alkyl, halogen, R ² is H, optionally substituted C _1-12 alkyl, halogen, R ³ is H, optionally substituted. C _1-12 alkyl, halogen, R ⁴ is H, optionally substituted C _1-12 alkyl, halogen, R ⁵ is H, optionally substituted C _1-12 alkyl, halogen. R ⁶ is H, optionally substituted C _1-12 alkyl, halogen, R ⁷ is H, optionally substituted C _1-12 alkyl, halogen, R ⁸ is H. , Arbitrarily substituted C _1-12 alkyl, halogen, R ⁹ is H, optionally substituted C _1-12 alkyl, halogen, R ¹⁹ is H, optionally substituted C _{1 ~ 12 Alkoxy} , -C (R ³⁴ ) (R ³⁵ ) -COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O) H, -C (R ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) -CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) -NR ⁴¹ R ⁴² , -C (R ³⁴ ) ( R ³⁵ ) C (O) -NR ⁴¹ OR ⁴⁰ , -C (O) R ²⁵ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C _{6 10} Aryl, optionally substituted C _3-8 cycloalkoxy, or R ³³ may form an arbitrarily substituted heterocycle, where R ²⁰ is H, optionally substituted C _1-12. Alkoxy, Haloalkane, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C ₆ -C ₁₀ aryl, or a _{C 3 to 8} cycloalkenyl optionally substituted, or together with ^{R 21,} may form a polycyclic ^{ring, R 21} is, _{C. 1 to} substituted H, optionally ₁₂ alkyl, halogen, -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C _{6 to} C ₁₀ aryl, optionally substituted C ₃ Heterocyclic rings may be formed with _{~ 8} cycloalkenyl, or with R ²⁰ or with R ^{22 , where R 22} is H, optionally substituted C _1-12 alkyl, halogen, -C ( O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C _{6 to} C ₁₀ aryl, optionally substituted C _{3 to 8} cycloalkenyl Or may form a polycyclic ring with ^{R 21} or with R ^{23 , where R 23} is H, optionally substituted C _1-12 alkyl, halogen, optionally substituted heterocycle. , _{C 3 to 8} cycloalkyl optionally substituted, optionally substituted _C 6 _{-C 10} aryl, or a _{C 3 to 8} cycloalkenyl optionally substituted, or together with ^{R 22,} a polycyclic ring May be formed, R ²⁴ is H, R ²⁵ is OH, OR ³⁰ , NR ²⁷ R ²⁸ , optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, Arbitrarily substituted heterocycles, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, R ²⁶ is H, optionally substituted C _{1 to 12} Alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, R. ²⁷ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally. _{C 3-8} cycloalkenyl substituted with, R ²⁸ is H, optionally substituted C _1-12 alkyl, optionally substituted C _{3 ~ 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, where R ²⁹ is H, optionally substituted. C _1-12 alkyl, OR ²⁶ , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optionally substituted C _{6 to} C ₁₀ aryl, or optionally _{C 3-8} cycloalkenyl substituted with, R ³⁰ is optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted. Substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, R ³¹ is H, optionally substituted C _{1 to 12} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, where R ³² is H, optionally substituted. C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl R ³³ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ Aryl, optionally substituted C _3-8 cycloalkenyl, or may form an arbitrarily substituted heterocycle with ^{R 19 , where R 34} is H, optionally substituted C _{1 to 12} alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl. R ³⁵ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or. Arbitrarily substituted C _3-8 cycloalkenyl, R ³⁶ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle. , Arbitrarily substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, R. ³⁷ is optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted. C _3-8 cycloalkenyl, R ³⁸ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally Substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, R ³⁹ is H, optionally substituted C _{1 to 12} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, where R ⁴⁰ is H, optionally substituted. C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl R ⁴¹ is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C _{6 to} C ₁₀ Aryl, or optionally substituted C _3-8 cycloalkenyl, where R ⁴² is H, optionally substituted C _1-12 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted. Heterocycle, optionally substituted C _{6 to} C ₁₀ aryl, or optionally substituted C _{3 to 8} cycloalkenyl, x is 1 or 2, and adamantyl is one or more C _{1 to 6} It can be optionally substituted by an alkyl group.

In another embodiment, the invention provides a catalyst represented by formula (V), where W is O and X ¹ is CF ₃ CO ₂ , CH ₃ CO ₂ , CH ₃ CH _2. CO _2, CFH ₂ CO ₂ , (CH ₃ ) ₃ CO ₂ , (CH ₃ ) ₂ CHCO ₂ , (CF ₃ ) ₂ (CH ₃ ) CO ₂ , (CF ₃ ) (CH ₃ ) ₂ CO ₂ , benzoate, Naftylate, tosylate, mesylate, or trifluoromethanesulfonate, R ¹ is H, linear or branched C _1-6 alkyl, or halogen, R ² is H, linear or branched C. _{1 to 6} alkyl or halogen, R ³ is H, linear or branched C _{1 to 6} alkyl, or halogen, R ⁴ is H, linear or branched C _{1 to 6} alkyl. , Or halogen, R ⁵ is H, linear or branched C _{1 to 6} alkyl, R ⁶ is H, linear or branched C _{1 to 6} alkyl, and R ⁷ is. H, straight chain or branched chain C _1-6 alkyl, R ⁸ is H or C _1-6 alkyl, R ⁹ is H, straight chain or branched chain C _1-6 alkyl. R ¹⁹ is H, phenyl, C ₁ to ₆ alkyl, -C (R ³⁴ ) (R ³⁵ ) COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O) H, -C (R ³⁴ ) ( R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , forming a 5, 6 or 7-membered heterocycle with ^{R 33 , where R 20} is H, linear or branched. C _1-16 alkyl, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) _2, -SR ³¹ , with pyridine, piperidine, imidazole, indridin, indazole, optionally substituted C _3-8 cycloalkyl, phenyl, naphthalene, cyclohexene, or R ²¹ . may form a ^{polycyclic, R 21} is, H, ^{phenyl, -NR} 27 ^{R 28,} straight-chain or branched _C 1 _{~ 6} alkyl, halogen, or together with ^{R 20} or R With ^22, may form a ^{polycyclic, R 22} is, H, linear or branched _{C 1 to 6} alkyl, ^{halogen, -C (O) R 25,} -OR 26, CN, -NR 27 R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) _2, -SR ³¹ , pyridine, piperidine, imidazole, indolidin , Indazole, optionally substituted C _3-8 cycloalkyl, phenyl, naphthalene, cyclohexene, or with R ²¹ or with R ²³ , where R ²³ is H, phenyl, linear. Alternatively, the branched chain C _{1 to 6} alkyl or can form a polycycle with ^{R 22 , where R 24} is H, linear or branched chain C _{1 to 6} alkyl, and R ²⁵ is. OH, OR ³⁰ , NR ²⁷ R ²⁸ , straight chain or branched chain C _1-6 alkyl, R ²⁶ is H, straight chain or branched chain C _1-6 alkyl, R ²⁷ is H, Straight chain or branched chain C _1-6 alkyl, R ²⁸ is H, straight chain or branched chain C _1-6 alkyl, R ²⁹ is H, straight chain or branched chain C _1-6 Alkyl, −NR ²⁷ R ²⁸ −, where R ³⁰ is optionally substituted C _1-6 alkyl, optionally substituted C _3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted. Is phenyl, or optionally substituted C _3-8 cycloalkenyl, R ³¹ is H, straight chain or branched chain C _1-6 alkyl, and R ³² is H, straight chain or branched chain. C _1-6 alkyl, R ³³ is H, linear or branched C _1-6 alkyl, or ^{together with R 19} , forms a 5-membered, 6-membered, or 7-membered heterocycle, R ^34. Is H, or linear or branched C _{1 to 6} alkyl, R ³⁵ is H, or linear or branched C _{1 to 6} alkyl, and R ³⁶ is H, linear or branched. a Edakusari _{C 1 to 6} ^{alkyl, R 37} is a linear or branched _{C 1 to 6} ^{alkyl, R 38} is H, or a linear or branched _{C 1 to 6} alkyl, R ³⁹ is H, linear or branched C _{1 to 6} alkyl, R ⁴⁰ is H, linear or branched C _{1 to 6} alkyl, and R ⁴¹ is H, linear or branched. Chain C _1-6 alkyl, R ⁴² is H, linear or branched chain C _1-6 alkyl, x is 1 or 2, and adamantyl is one or more. It can be optionally substituted by the C _{1-6 alkyl groups above.}

In one embodiment, the invention provides a catalyst represented by formula (V), where W is O and X ¹ is CF ₃ CO ₂ , CH ₃ CO ₂ , CH ₃ CH ₂ CO. _2, CFH ₂ CO ₂ , (CH ₃ ) ₃ CO ₂ , (CH ₃ ) ₂ CHCO ₂ , (CF ₃ ) ₂ (CH ₃ ) CO ₂ , (CF ₃ ) (CH ₃ ) ₂ CO ₂ , benzoate, naphthyl Rate, tosylate, mesylate, or trifluoromethanesulfonate, R ¹ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or H, and R ² is. Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or H, where R ³ is H, Me, Et, i-Pr, n-Pr, n-Bu. , T-Bu, or s-Bu, R ⁴ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ⁵ is H. , F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ⁶ is H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, where R ⁷ is H, F, Cl, Br, I, Me, Et, i-Pr, n. -Pr, n-Bu, t-Bu, or s-Bu, where R ⁸ is H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu, t- Bu, or s-Bu, where R ⁹ is H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu. R ¹⁹ is, H, phenyl, _{C 1} - ₆ ^{alkyl, -C (R 34) (R} 35) COOR 36, -C (R 34) (R 35) C (O) H, -C (R 34) ( R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , where R ²⁰ is H, F, Cl, Br, I, Me, Et, i-Pr, n-Pr, n-Bu. , T-Bu, s-Bu, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , pyridine, piperidine, imidazole, indridin, indazole, optionally substituted C _3-8 cycloalkyl, phenyl, naphthalene, or cyclohexene, where R ²¹ is H, phenyl, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, -NR ²⁷ R ²⁸ F, Cl, Br, or I, where R ²² is H, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O) _x R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , or- SR ³¹ - a ^{and, R 23} is H, F, Cl, Br, I, phenyl, Me, Et, i-Pr , n-Pr, n-Bu, t-Bu, or s-Bu, R ²⁴ is H, R ²⁴ is H or Me, R ²⁵ is OH, OR ³⁰ , NR ²⁷ R ²⁸ , Me, Et, or i-Pr, and R ²⁶ is H, Me, Et. , I-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, R ²⁷ is H, Me, Et, or i-Pr, and R ²⁸ is H, Me, Et. , I-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, where R ²⁹ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or -NR ²⁷ R ²⁸ , R ³⁰ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ³¹ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, R ³² is Me, Et, n-Pr, or H, and R ³³ is H, Me, Et, is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, s-Bu, or together with ^{R 19} morpholino, thio - morpholino, pyrrolidino, piperidino, or piperazino forms a ring , R ³⁴ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ³⁵ is H, or Me, Et, i-Pr, n. -Pr, n-Bu, t-Bu, or s-Bu, and R ³⁶ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu. , R ³⁷ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ³⁸ is H or Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, where R ³⁹ is , H, a Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or ^{s-Bu, R 40} is, H, Me, Et, i -Pr, n-Pr, n- Bu, t-Bu, or s-Bu, R ⁴¹ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ⁴² is. H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, x is 1 or 2, and adamantyl is optionally substituted by one or more Me groups. Can be done.

In one embodiment, the invention provides a catalyst represented by formula (V), where W is O, X ¹ is nitrate, R ¹ is H, and R ² is H. Yes, R ³ is H, R ⁴ is H, R ⁵ is H, F, Me, Et, or i-Pr, and R ⁶ is H, F, Me, Et, or i-. Pr, R ⁷ is H, F, Me, Et, or i-Pr, R ⁸ is H, F, Me, Et, or i-Pr, and R ⁹ is H, F, Me, is Et, or ^{i-Pr, R 19} is, H, phenyl, _{C 1} - ₆ ^{alkyl, -C (R 34) (R} 35) COOR 36, -C (R 34) (R 35) C ( O) H, -C (R ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R) ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , where R ²⁰ is H, F, Me, Et, or i-Pr. , R ²¹ is H, F, Me, Et, or i-Pr, and R ²² is H, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ ,- ^{_{CF 3, -S (O) x}} R 29, -P (O) (OH) 2, -OP (O) (OH) 2, or ^{-SR 31} - a ^{and, R 23} is, H, F, Me, Et, or i-Pr, R ²⁴ is H, R ²⁵ is OH, OR ³⁰ , NR ²⁷ R ²⁸ , Me, Et, or i-Pr, and R ²⁶ is H, Me, Et. , I-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, R ²⁷ is H, Me, Et, or i-Pr, and R ²⁸ is H, Me, Et. a i-Pr, n-Pr, n-Bu, t-Bu, or ^{s-Bu, R 29} is, H, Me, Et, i -Pr, n-Pr, n-Bu, t-Bu, s-Bu, or -NR ²⁷ R ²⁸ , R ³⁰ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, R ³¹ is H, Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, R ³² is Me, Et, n-Pr, or H, and R ³⁴ is H, F, Me, Et, or i-Pr, R ³⁵ is H, F, Me, Et, or i-Pr, and R ³⁶ is H, F. , Me, Et, or i-Pr, R ³⁷ is Me, Et, i-Pr, n-Pr, n-Bu, t-Bu, or s-Bu, and R ³⁸ is H, F. , Me, Et, or i-Pr, R ³⁹ is H, F, Me, Et, or i-Pr, and R ⁴⁰ is H, F, Me, Et, or i-Pr. Yes, R ⁴¹ is H, F, Me, Et, or i-Pr, and R ⁴² is H, F, Me, Et, or i-Pr.

In one embodiment, the invention provides a catalyst represented by formula (V), where W is O, X ¹ is nitrate, R ¹ is H, and R ² is H. Yes, R ³ is H, R ⁴ is H, R ⁵ is Me, R ⁶ is H, R ⁷ is Me, R ⁸ is H, and R ⁹ is Me. , R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

In one embodiment, the invention provides a catalyst represented by formula (V), where W is O, X ¹ is nitrate, R ¹ is H, and R ² is H. Yes, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i -Pr, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

から選択される。 In one embodiment, the invention provides a compound of formula (V).

Is selected from.

It will be appreciated that the catalyst used in the reaction (ie, "catalyst retention") depends on various factors such as the attributes of the reactants used and the reaction conditions. Therefore, it is understood that the catalyst retention amount can be optimally and independently selected for each reaction. However, in general, the catalyst is an amount ranging from a small amount of about 0.1 ppm, 1 ppm or 5 ppm to a large amount of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm or 1000 ppm with respect to the amount of the olefin substrate. Will exist in.

The catalyst generally ranges from as low as about 0.00001 mol%, 0.0001 mol%, or 0.0005 mol% to about 0.001 mol%, 0.0015 mol%, 0.0025 mol%, 0.0025 mol%, 0. It is present in amounts up to the high range of 005 mol%, 0.01 mol%, 0.02 mol%, 0.05 mol%, or 0.1 mol%.

When expressed as an olefin to catalyst molar ratio, the catalyst (“olefin to catalyst ratio”) is generally about 1,000,000: 1, 1,000,000: 1, 500,000: 1, or 200. Amounts in the high range of about 100,000: 1, 60,000: 1, 50,000: 1, 45,000, from the low range of 00: 1, 1,40,000: 1, 30,000: 1, It exists in the ratio of 20,000: 1, 10,000: 1, 5,000: 1, or 1,000: 1.
Embodiment

These and other aspects of the invention will be apparent to those skilled in the art in light of the following detailed description and examples.

The present invention has at least one carbon-carbon double bond (eg, product internal olefin) in 95/5, or 96/4, or 97/3, or 98/2, or 99/1 Z / E. Provided are a method of producing a compound having a selectivity ratio (ie, product, olefin product, eg, cross metathesis). In some cases, 100% of at least one carbon-carbon double bond produced in the cross metathesis reaction has a Z configuration.

（式中、Ｒ^ｚは、

から選択され、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下、又は式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒ^ｖは

から選択され、立体保持ルテニウムオレフィンメタセシス触媒は、式（Ｉ）によって表され、

Ｘは、Ｏ又はＳであり、
Ｙは、Ｏ又はＳであり、
Ｚは、Ｎ又はＣＲ^３２であり、
Ｗは、Ｏ、ハロゲン、ＮＲ^３３又はＳであり、
Ｒ^１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２と共にスピロ化合物を形成してもよく、又はＲ^３と共に若しくはＲ^４と共に、多環式環を形成してもよく、
Ｒ^２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１と共にスピロ化合物を形成してもよく、又はＲ^３と共に若しくはＲ^４と共に、多環式環を形成してもよく、
Ｒ^３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２と共に若しくはＲ^１と共に、多環式環を形成してもよく、又はＲ^４と共にスピロ化合物を形成してもよく、
Ｒ^４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^３と共にスピロ化合物を形成してもよく、又はＲ^２と共に若しくはＲ^１と共に、多環式環を形成してもよく、
Ｒ^５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^６と共に、任意に置換された多環式環を形成してもよく、
Ｒ^６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^５と共に若しくはＲ^７と共に、任意に置換された多環式環を形成してもよく、
Ｒ^７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^６と共に若しくはＲ^８と共に、任意に置換された多環式環を形成してもよく、
Ｒ^８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^７と共に若しくはＲ^９と共に、任意に置換された多環式環を形成してもよく、
Ｒ^９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^８と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１１と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１０と共に若しくはＲ^１２と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１１と共に若しくはＲ^１３と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１４と共に若しくはＲ^１２と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１３と共に、多環式環を形成してもよく、
Ｒ^１５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１６と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１５と共に若しくはＲ^１７と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１８と共に若しくはＲ^１６と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１７と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、−Ｃ（Ｒ^３４）（Ｒ^３５）ＣＯＯＲ^３６、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）Ｈ、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）Ｒ^３７、−Ｃ（Ｒ^３４）（Ｒ^３５）ＣＲ^３８（ＯＲ^３９）（ＯＲ^４０）、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）ＮＲ^４１Ｒ^４２、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）ＮＲ^４１ＯＲ^４０、−Ｃ（Ｏ）Ｒ^２５、任意に置換された複素環であり、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニル、又はＲ^３３と共に、任意に置換された複素環を形成してもよく、又はＷがハロゲンである場合にはゼロであり、
Ｒ^２０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２１と共に、多環式環を形成してもよく、
Ｒ^２１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２０と共に若しくはＲ^２２と共に、多環式環を形成してもよく、
Ｒ^２２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２１と共に若しくはＲ^２３と共に、多環式環を形成してもよく、
Ｒ^２３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２２と共に、多環式環を形成してもよく、
Ｒ^２４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２５は、ＯＨ、ＯＲ^３０、ＮＲ^２７Ｒ^２８、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ＯＲ^２６、−ＮＲ^２７Ｒ^２８、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３０は、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１９と共に、任意に置換された複素環を形成してもよく、
Ｒ^３４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３７は、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
ｘは１又は２であり、式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒は、

［式中、
Ｗは、Ｏ、ハロゲン、ＮＲ^３３又はＳであり、
Ｘ^１は、水素、ハロゲン化物、硝酸塩、任意に置換されたＣ_１〜Ｃ_２０アルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_１〜Ｃ_２０アルコキシ、任意に置換されたＣ_１〜Ｃ_２０アルキルカルボキシレート、任意に置換されたＣ_５〜Ｃ_２４アリールオキシ、任意に置換されたＣ_２〜Ｃ_２０アルコキシカルボニル、任意に置換されたＣ_６〜Ｃ_２４アリールオキシカルボニル、任意に置換されたＣ_６〜Ｃ_２４アリールカルボキシレート、任意に置換されたＣ_２〜Ｃ_２４アシル、任意に置換されたＣ_２〜Ｃ_２４アシルオキシ、任意に置換されたＣ_１〜Ｃ_２０アルキルスルホナト、任意に置換されたＣ_５〜Ｃ_２４アリールスルホナト、任意に置換されたＣ_１〜Ｃ_２０アルキルスルファニル、任意に置換されたＣ_５〜Ｃ_２４アリールスルファニル、任意に置換されたＣ_１〜Ｃ_２０アルキルスルフィニル、又は任意に置換されたＣ_５〜Ｃ_２４アリールスルフィニル；
Ｒ^１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２と共にスピロ化合物を形成してもよく、又はＲ^３と共に若しくはＲ^４と共に、多環式環を形成してもよく、
Ｒ^２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１と共にスピロ化合物を形成してもよく、又はＲ^３と共に若しくはＲ^４と共に、多環式環を形成してもよく、
Ｒ^３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２と共に若しくはＲ^１と共に、多環式環を形成してもよく、又はＲ^４と共にスピロ化合物を形成してもよく、
Ｒ^４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^３と共にスピロ化合物を形成してもよく、又はＲ^２と共に若しくはＲ^１と共に、多環式環を形成してもよく、
Ｒ^５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^６と共に、任意に置換された多環式環を形成してもよく、
Ｒ^６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^５と共に若しくはＲ^７と共に、任意に置換された多環式環を形成してもよく、
Ｒ^７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^６と共に若しくはＲ^８と共に、任意に置換された多環式環を形成してもよく、
Ｒ^８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^７と共に若しくはＲ^９と共に、任意に置換された多環式環を形成してもよく、
Ｒ^９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^８と共に、任意に置換された多環式環を形成してもよく、
Ｒ^１９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、−Ｃ（Ｒ^３４）（Ｒ^３５）ＣＯＯＲ^３６、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）Ｈ、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）Ｒ^３７、−Ｃ（Ｒ^３４）（Ｒ^３５）ＣＲ^３８（ＯＲ^３９）（ＯＲ^４０）、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）ＮＲ^４１Ｒ^４２、−Ｃ（Ｒ^３４）（Ｒ^３５）Ｃ（Ｏ）ＮＲ^４１ＯＲ^４０、−Ｃ（Ｏ）Ｒ^２５、任意に置換された複素環であり、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜２４アリール、任意に置換されたＣ_３〜８シクロアルケニル、又はＲ^３３と共に、任意に置換された複素環を形成してもよく、又はＷがハロゲンである場合にはゼロであり、
Ｒ^２０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２１と共に、多環式環を形成してもよく、
Ｒ^２１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２０と共に若しくはＲ^２２と共に、多環式環を形成してもよく、
Ｒ^２２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２１と共に若しくはＲ^２３と共に、多環式環を形成してもよく、
Ｒ^２３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^２２と共に、多環式環を形成してもよく、
Ｒ^２４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ハロゲン、−Ｃ（Ｏ）Ｒ^２５、−ＯＲ^２６、ＣＮ、−ＮＲ^２７Ｒ^２８、ＮＯ_２、−ＣＦ_３、−Ｓ（Ｏ）_ｘＲ^２９、−Ｐ（Ｏ）（ＯＨ）_２、−ＯＰ（Ｏ）（ＯＨ）_２、−ＳＲ^３１、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２５は、ＯＨ、ＯＲ^３０、ＮＲ^２７Ｒ^２８、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２７は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^２９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、ＯＲ^２６、−ＮＲ^２７Ｒ^２８、任意に置換されたヘテロ環、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３０は、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３３は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであるか、又はＲ^１９と共に、任意に置換された複素環を形成してもよく、
Ｒ^３４は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３５は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３６は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３７は、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３８は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^３９は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４０は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４１は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
Ｒ^４２は、Ｈ、任意に置換されたＣ_１〜２４アルキル、任意に置換されたＣ_３〜８シクロアルキル、任意に置換されたヘテロ環、任意に置換されたＣ_５〜Ｃ_２４アリール、又は任意に置換されたＣ_３〜８シクロアルケニルであり、
ｘは、１又は２である。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. Have sex)
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

In the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) or with a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) between cis-octene-1-ol. It formed in the cross metathesis reaction, wherein, R ^v is

The steric retaining ruthenium olefin metathesis catalyst selected from is represented by the formula (I).

X is O or S,
Y is O or S,
Z is N or CR ³²
W is O, halogen, NR ³³ or S.
R ¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or a spiro compound may be formed with ^{R 2} , or polycyclic with ^{R 3} or with R ^4. You may form a formula ring,
R ² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or a spiro compound may be formed with ^{R 1} , or polycyclic with ^{R 3} or with R ^4. You may form a formula ring,
R ³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ² or with R ¹ may form a polycyclic ring, or R ⁴ May form a spiro compound with
R ⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or a spiro compound may be formed with ^{R 3} , or polycyclic with ^{R 2} or with R ^1. You may form a formula ring,
R ⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁶ to form an optionally substituted polycyclic ring.
R ⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ⁵ or together with R ^7, may form a polycyclic ring which is optionally substituted ,
R ⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ⁶ or with R ^8, may form a polycyclic ring which is optionally substituted ,
R ⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ⁷ or with R ^9, may form a polycyclic ring which is optionally substituted ,
R ⁹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁸ to form an optionally substituted polycyclic ring.
R ¹⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹¹ may form an optionally substituted polycyclic ring.
R ¹¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ¹⁰ or together with R ^12, may form a polycyclic ring which is optionally substituted ,
R ¹² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ¹¹ or together with R ^13, may form a polycyclic ring which is optionally substituted ,
R ¹³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ¹⁴ or together with R ^12, may form a polycyclic ring which is optionally substituted ,
R ¹⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹³ may form a polycyclic ring.
R ¹⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹⁶ to form an arbitrarily substituted polycyclic ring.
R ¹⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹⁵ or with R ¹⁷ to form an arbitrarily substituted polycyclic ring. Often,
R ¹⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹⁸ or with R ¹⁶ to form an arbitrarily substituted polycyclic ring. Often,
R ¹⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹⁷ may form an arbitrarily substituted polycyclic ring.
R ¹⁹ is H, optionally substituted C _1-24 alkyl, -C (R ³⁴ ) (R ³⁵ ) COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O) H, -C (R). ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , -C (O) R ²⁵ , optionally substituted heterocycle, optionally substituted C _3-8 cyclo Arbitrarily substituted heterocycles may be formed with alkyl, optionally substituted C _{5 to 24} aryl, optionally substituted C _{3 to 8} cycloalkenyl, or R ³³ , or W is a halogen. If it is zero,
R ²⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ may form a polycyclic ring.
R ²¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²⁰ or with R ²² may form a polycyclic ring.
R ²² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ or with R ²³ may form a polycyclic ring.
R ²³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²² may form a polycyclic ring.
R ²⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl.
R ²⁵ was OH, OR ³⁰ , NR ²⁷ R ²⁸ , optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted. C _{5 to} C ₂₄ aryl, or optionally substituted C _{3 to 8} cycloalkenyl,
R ²⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ²⁷ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ²⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ²⁹ is H, optionally substituted C _{1 to 24} alkyl, OR ²⁶ , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted. C _{5 to} C ₂₄ aryl, or optionally substituted C _{3 to 8} cycloalkenyl.
R ³⁰ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or optionally. Substituted C _3-8 cycloalkenyl,
R ³¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³³ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or It may be an optionally substituted C _3-8 cycloalkenyl, or ^{together with R 19} , an arbitrarily substituted heterocycle may be formed.
R ³⁴ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³⁵ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³⁷ can be optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or optionally. Substituted C _3-8 cycloalkenyl,
R ³⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³⁹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ⁴⁰ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ⁴¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ⁴² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
x is 1 or 2, and the Z-selective ruthenium olefin metathesis catalyst represented by the formula (V) is

[During the ceremony,
W is O, halogen, NR ³³ or S.
X ¹ is hydrogen, halide, nitrate, optionally substituted C _{1 to} C ₂₀ alkyl, optionally substituted C _{5 to} C ₂₄ aryl, optionally substituted C _{1 to} C ₂₀ alkoxy, optionally substituted. C _{1 to} C ₂₀ alkyl carboxylates, optionally substituted C _{5 to} C ₂₄ aryloxy, optionally substituted C _{2 to} C ₂₀ alkoxycarbonyl, optionally substituted C _{6 to} C ₂₄ aryloxycarbonyl , Arbitrarily substituted C _{6 to} C ₂₄ arylcarboxylate, optionally substituted C _{2 to} C ₂₄ acyl, optionally substituted C _{2 to} C ₂₄ acyloxy, optionally substituted C _{1 to} C ₂₀ alkyl Alkoxynat, optionally substituted C _{5 to} C ₂₄ aryl sulfonato, optionally substituted C _{1 to} C ₂₀ alkylsulfanyl, optionally substituted C _{5 to} C ₂₄ aryl sulfanyl, optionally substituted C ₁ -C ₂₀ alkylsulfinyl, or optionally substituted _C 5 _{-C 24} arylsulfinyl;
R ¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or a spiro compound may be formed with ^{R 2} , or polycyclic with ^{R 3} or with R ^4. You may form a formula ring,
R ² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or a spiro compound may be formed with ^{R 1} , or polycyclic with ^{R 3} or with R ^4. You may form a formula ring,
R ³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ² or with R ¹ may form a polycyclic ring, or R ⁴ May form a spiro compound with
R ⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or a spiro compound may be formed with ^{R 3} , or polycyclic with ^{R 2} or with R ^1. You may form a formula ring,
R ⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁶ to form an optionally substituted polycyclic ring.
R ⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ⁵ or together with R ^7, may form a polycyclic ring which is optionally substituted ,
R ⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ⁶ or with R ^8, may form a polycyclic ring which is optionally substituted ,
R ⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C ₅ -C ₂₄ aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together with R ⁷ or with R ^9, may form a polycyclic ring which is optionally substituted ,
R ⁹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁸ to form an optionally substituted polycyclic ring.
R ¹⁹ is H, optionally substituted C _1-24 alkyl, -C (R ³⁴ ) (R ³⁵ ) COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O) H, -C (R). ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , -C (O) R ²⁵ , optionally substituted heterocycle, optionally substituted C _3-8 cyclo Arbitrarily substituted heterocycles may be formed with alkyl, optionally substituted C _{5 to 24} aryl, optionally substituted C _{3 to 8} cycloalkenyl, or R ³³ , or W is a halogen. If it is zero,
R ²⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ may form a polycyclic ring.
R ²¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²⁰ or with R ²² may form a polycyclic ring.
R ²² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ or with R ²³ may form a polycyclic ring.
R ²³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²² may form a polycyclic ring.
R ²⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl.
R ²⁵ was OH, OR ³⁰ , NR ²⁷ R ²⁸ , optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted. C _{5 to} C ₂₄ aryl, or optionally substituted C _{3 to 8} cycloalkenyl,
R ²⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ²⁷ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ²⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ²⁹ is H, optionally substituted C _{1 to 24} alkyl, OR ²⁶ , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted. C _{5 to} C ₂₄ aryl, or optionally substituted C _{3 to 8} cycloalkenyl.
R ³⁰ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or optionally. Substituted C _3-8 cycloalkenyl,
R ³¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³³ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or It may be an optionally substituted C _3-8 cycloalkenyl, or ^{together with R 19} , an arbitrarily substituted heterocycle may be formed.
R ³⁴ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³⁵ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³⁷ can be optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or optionally. Substituted C _3-8 cycloalkenyl,
R ³⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ³⁹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ⁴⁰ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ⁴¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
R ⁴² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to} C ₂₄ aryl, or Arbitrarily substituted C _3-8 cycloalkenyl,
x is 1 or 2.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下、又は本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下でシス−オクテン−１−オールと共に、供する工程を含み、式中、
Ｒ^ｖは、

から選択される。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

In the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, or in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein. Including the step of serving with cis-octen-1-ol below, in the formula,
^Rv is

Is selected from.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含む。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

Includes subjecting to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含む。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

Includes subjecting to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含む。 In one embodiment, the present invention is at least one delta ¹² represented by formula (III) ^- provides a process for preparing prostaglandin J product,

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

Includes subjecting to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含む。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

Includes subjecting to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含む。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

Includes subjecting to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含む。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

Includes subjecting to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含む。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

Includes subjecting to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含む。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

Includes subjecting to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒ^ｖは

である。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, R in the formula. ^v is

Is.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒｖは

である。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein, in the formula, Rv is

Is.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒ^ｖは

である。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, R in the formula. ^v is

Is.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒｖは

から選択される。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein, in the formula, Rv is

Is selected from.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒｖは

である。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, Rv in the formula. teeth

Is.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒｖは

から選択される。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein, in the formula, Rv is

Is selected from.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒ^ｖは

である。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, R in the formula. ^v is

Is.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、本明細書に定義される式（Ｖ）に表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、Ｒｖは

である。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst of formula (V) as defined herein, in the formula, Rv is

Is.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

から選択される）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１０はｉ−Ｐｒであり、Ｒ^１１はＨであり、Ｒ^１２はＨであり、Ｒ^１３はＨであり、Ｒ^１４はｉ−Ｐｒであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

In the presence of a conformational ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, including subjecting to a cross-metathesis reaction with cis-5-octene-1-ol. , In the formula, X is S, Y is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, and R ¹⁰ is i-. Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is i-Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ Is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

から選択される）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１０はＭｅであり、Ｒ^１１はＨであり、Ｒ^１２はＭｅであり、Ｒ^１３はＨであり、Ｒ^１４はＭｅであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

In the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, including subjecting to a cross-metathesis reaction with cis-5-octene-1-ol. , In the formula, X is S, Y is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is Me, R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ Is H, R ¹² is Me, R ¹³ is H, R ¹⁴ is Me, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, and R ¹⁸ is. Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

から選択される）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 (In the formula, ^Rv is

To be subjected to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein. In the formula, W is O, X ¹ is nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is i. -Pr, R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁹ is i-Pr, R ²⁰ is H. , R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

から選択される）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 (In the formula, ^Rv is

To be subjected to a cross-metathesis reaction with cis-5-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein. In the formula, W is O, X ¹ is nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is Me. R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁹ is i-Pr, R ²⁰ is H, and R ²¹ is. H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（式中、Ｒ^ｚは、

から選択され、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を投入することによって、

（式中Ｒ^Ｖは、

から選択される）、
テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１０はｉ−Ｐｒであり、Ｒ^１１はＨであり、Ｒ^１２はＨであり、Ｒ^１３はＨであり、Ｒ^１４はｉ−Ｐｒであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. Have sex),
By adding the alcohol product of formula (III)

(Wherein ^{R V} is,

(Selected from),
Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction between cis-octene-1-ol in the presence of a conformational ruthenium olefin metathesis catalyst represented by formula (I), where X is S and Y is. S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is i-Pr. R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is i-Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, and so on. R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（式中、Ｒ^ｚは、

から選択され、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を投入することによって、

（式中Ｒ^Ｖは、

から選択される）、
テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１０はＭｅであり、Ｒ^１１はＨであり、Ｒ^１２はＭｅであり、Ｒ^１３はＨであり、Ｒ^１４はＭｅであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. Have sex),
By adding the alcohol product of formula (III)

(Wherein ^{R V} is,

(Selected from),
Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a conformational ruthenium olefin metathesis catalyst represented by formula (I), where X is S and Y is. S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is Me. , R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H, R ¹² is Me, and so on. R ¹³ is H, R ¹⁴ is Me, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, and R ¹⁹ is i-Pr. , R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（式中、Ｒ^ｚは、

から選択され、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を投入することによって、

（式中Ｒ^Ｖは、

から選択される）、
テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. Have sex),
By adding the alcohol product of formula (III)

(Wherein ^{R V} is,

(Selected from),
Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction between cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V), where W is O and X. ¹ is a nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is Me, R ⁶ is H, R ⁷ Is Me, R ⁸ is H, R ⁹ is Me, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H and R ²⁴ is H.

（式中、Ｒ^ｚは、

から選択され、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を投入することによって、

（式中Ｒ^Ｖは、

から選択される）、
テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入するか、又はピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. Have sex),
By adding the alcohol product of formula (III)

(Wherein ^{R V} is,

(Selected from),
Includes steps to inject into oxidation in the presence of tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate, or into oxidation in the presence of pyridinium chlorochromate and sodium chlorite. , The alcohol product of formula (III) is the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V), where W is O and X. ¹ is a nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, and so on. R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, and R ²² is H. R ²³ is H and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１０はＭｅであり、Ｒ^１１はＨであり、Ｒ^１２はＭｅであり、Ｒ^１３はＨであり、Ｒ^１４はＭｅであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

In the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, it comprises subjecting it to a cross metathesis reaction with cis-5-octene-1-ol. Among them, X is S, Y is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, and R ⁴ is. H, R ⁵ is Me, R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H. R ¹² is Me, R ¹³ is H, R ¹⁴ is Me, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, and R ¹⁸ is Cl. Yes, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１０はｉ−Ｐｒであり、Ｒ^１１はＨであり、Ｒ^１２はＨであり、Ｒ^１３はＨであり、Ｒ^１４はｉ−Ｐｒであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

In the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, it comprises subjecting it to a cross-metathesis reaction with cis-5-octene-1-ol. Among them, X is S, Y is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, and R ⁴ is. H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr. Yes, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is i-Pr, R ¹⁵ is Cl, R ¹⁶ is H, and R ¹⁷ is H. R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is. It is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１０はＭｅであり、Ｒ^１１はＨであり、Ｒ^１２はＭｅであり、Ｒ^１３はＨであり、Ｒ^１４はＭｅであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ), The base material represented by the formula (II),

(In the formula, ^Rv is

In the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, it comprises subjecting it to a cross metathesis reaction with cis-5-octene-1-ol. Among them, X is S, Y is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, and R ⁴ is. H, R ⁵ is Me, R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H. R ¹² is Me, R ¹³ is H, R ¹⁴ is Me, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, and R ¹⁸ is Cl. Yes, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１０はｉ−Ｐｒであり、Ｒ^１１はＨであり、Ｒ^１２はＨであり、Ｒ^１３はＨであり、Ｒ^１４はｉ−Ｐｒであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ), The base material represented by the formula (II),

(In the formula, ^Rv is

In the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, it comprises subjecting it to a cross-metathesis reaction with cis-5-octene-1-ol. Among them, X is S, Y is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, and R ⁴ is. H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr. Yes, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is i-Pr, R ¹⁵ is Cl, R ¹⁶ is H, and R ¹⁷ is H. R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is. It is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

In the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein, it comprises subjecting it to a cross-metathesis reaction with cis-5-octene-1-ol. In the formula, W is O, X ¹ is nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is Me. , R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H. Yes, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ), The base material represented by the formula (II),

(In the formula, ^Rv is

In the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein, it comprises subjecting it to a cross-metathesis reaction with cis-5-octene-1-ol. In the formula, W is O, X ¹ is nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is i-Pr. R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ), The base material represented by the formula (II),

(In the formula, ^Rv is

In the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein, it comprises subjecting it to a cross-metathesis reaction with cis-5-octene-1-ol. In the formula, W is O, X ¹ is nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is i-Pr. R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

In the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V) as defined herein, it comprises subjecting it to a cross-metathesis reaction with cis-5-octene-1-ol. In the formula, W is O, X ¹ is nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is Me. , R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H. Yes, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）に表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１０はＭｅであり、Ｒ^１１はＨであり、Ｒ^１２はＭｅであり、Ｒ^１３はＨであり、Ｒ^１４はＭｅであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ), The base material represented by the formula (II),

(In the formula, ^Rv is

In the presence of the conformational ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, it comprises subjecting it to a cross metathesis reaction with cis-5-octene-1-ol. Among them, X is S, Y is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, and R ⁴ is. H, R ⁵ is Me, R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H. R ¹² is Me, R ¹³ is H, R ¹⁴ is Me, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, and R ¹⁸ is Cl. Yes, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩ）によって表される基材を、

（式中、Ｒ^ｖは

である）本明細書に定義される式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下で、シス−５−オクテン−１−オールとの交差メタセシス反応に供することを含み、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１０はｉ−Ｐｒであり、Ｒ^１１はＨであり、Ｒ^１２はＨであり、Ｒ^１３はＨであり、Ｒ^１４はｉ−Ｐｒであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention provides a method for producing at least one alcohol product represented by formula (III).

(At least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. ),
The base material represented by the formula (II) is

(In the formula, ^Rv is

In the presence of a steric retaining ruthenium olefin metathesis catalyst represented by formula (I) as defined herein, it comprises subjecting it to a cross-metathesis reaction with cis-5-octene-1-ol. Among them, X is S, Y is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, and R ⁴ is. H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr. Yes, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is i-Pr, R ¹⁵ is Cl, R ¹⁶ is H, and R ¹⁷ is H. R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is. It is H.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を

（式中、Ｒ^ｖは

である）テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１０はｉ−Ｐｒであり、Ｒ^１１はＨであり、Ｒ^１２はＨであり、Ｒ^１３はＨであり、Ｒ^１４はｉ−Ｐｒであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of equation (III)

(In the formula, ^Rv is

The alcohol product of formula (III) is represented by formula (II), comprising the step of injecting tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate into oxidation in the presence of monohydrate. With the base material to be

Formed during a cross-metathesis reaction between cis-octene-1-ol in the presence of a conformational ruthenium olefin metathesis catalyst represented by formula (I), where X is S and Y is. S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is i-Pr. R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is i-Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, and so on. R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を、

（式中、Ｒ^ｖは

である）テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１０はＭｅであり、Ｒ^１１はＨであり、Ｒ^１２はＭｅであり、Ｒ^１３はＨであり、Ｒ^１４はＭｅであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of formula (III),

(In the formula, ^Rv is

The alcohol product of formula (III) is represented by formula (II), comprising the step of injecting tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate into oxidation in the presence of monohydrate. With the base material to be

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a conformational ruthenium olefin metathesis catalyst represented by formula (I), where X is S and Y is. S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is Me. , R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H, R ¹² is Me, and so on. R ¹³ is H, R ¹⁴ is Me, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, and R ¹⁹ is i-Pr. , R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（式中、Ｒ^ｚは

から選択され、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、式（ＩＩＩ）のアルコール生成物を、式中、Ｒ^Ｖは

である

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１０はｉ−Ｐｒであり、Ｒ^１１はＨであり、Ｒ^１２はＨであり、Ｒ^１３はＨであり、Ｒ^１４はｉ−Ｐｒであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. having sex), the alcohol product of formula (III), wherein, ^{R V} is

Is

The alcohol product of formula (III) comprises the steps of injecting tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate into oxidation in the presence of the group represented by formula (II). With wood

Formed during a cross-metathesis reaction between cis-octene-1-ol in the presence of a conformational ruthenium olefin metathesis catalyst represented by formula (I), where X is S and Y is. S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is i-Pr. R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is i-Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, and so on. R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（式中、Ｒ^ｚは

から選択され、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、式（ＩＩＩ）のアルコール生成物を、（式中、Ｒ^ｖは

である）

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１０はＭｅであり、Ｒ^１１はＨであり、Ｒ^１２はＭｅであり、Ｒ^１３はＨであり、Ｒ^１４はＭｅであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. The alcohol product of formula (III) (in the formula, R ^v is

Is)

The alcohol product of formula (III) comprises the steps of injecting tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate into oxidation in the presence of the group represented by formula (II). With wood

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a conformational ruthenium olefin metathesis catalyst represented by formula (I), where X is S and Y is. S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is Me. , R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H, R ¹² is Me, and so on. R ¹³ is H, R ¹⁴ is Me, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, and R ¹⁹ is i-Pr. , R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（式中、Ｒ^ｚは、

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を、（式中、Ｒ^Ｖは

である）

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of formula (III), (in formula, ^RV is

Is)

The alcohol product of formula (III) comprises the steps of injecting tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate into oxidation in the presence of the group represented by formula (II). With wood

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V), where W is O and X. ¹ is a nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, and so on. R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, and R ²² is H. R ²³ is H and R ²⁴ is H.

（式中、Ｒ^ｚは、

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を、（式中、Ｒ^Ｖは

である）

テトラプロピルアンモニウムペルルテネート及び４−メチルモルホリンＮ−オキシド一水和物の存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of formula (III), (in formula, ^RV is

Is)

The alcohol product of formula (III) comprises the steps of injecting tetrapropylammonium perrutenate and 4-methylmorpholine N-oxide monohydrate into oxidation in the presence of the group represented by formula (II). With wood

Formed during a cross-metathesis reaction between cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V), where W is O and X. ¹ is a nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is Me, R ⁶ is H, R ⁷ Is Me, R ⁸ is H, R ⁹ is Me, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H and R ²⁴ is H.

（式中、Ｒ^ｚは

から選択され、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を、（式中、Ｒ^Ｖは

である）

ピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. Have sex),
The alcohol product of formula (III), (in formula, ^RV is

Is)

The alcohol product of formula (III) comprises a step of subjecting to oxidation in the presence of pyridinium chlorochromate and sodium chlorite, with the substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V), where W is O and X. ¹ is a nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, and so on. R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, and R ²² is H. R ²³ is H and R ²⁴ is H.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を、（式中、Ｒ^Ｖは

である）

ピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｖ）によって表されるＺ選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＷはＯであり、Ｘ^１は硝酸塩であり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of formula (III), (in formula, ^RV is

Is)

The alcohol product of formula (III) comprises a step of subjecting to oxidation in the presence of pyridinium chlorochromate and sodium chlorite, with the substrate represented by formula (II).

Formed during a cross-metathesis reaction between cis-octene-1-ol in the presence of a Z-selective ruthenium olefin metathesis catalyst represented by formula (V), where W is O and X. ¹ is a nitrate, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is Me, R ⁶ is H, R ⁷ Is Me, R ⁸ is H, R ⁹ is Me, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H and R ²⁴ is H.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を、（式中、Ｒ^Ｖは

である）

ピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体保持ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はｉ−Ｐｒであり、Ｒ^６はＨであり、Ｒ^７はＨであり、Ｒ^８はＨであり、Ｒ^９はｉ−Ｐｒであり、Ｒ^１０はｉ−Ｐｒであり、Ｒ^１１はＨであり、Ｒ^１２はＨであり、Ｒ^１３はＨであり、Ｒ^１４はｉ−Ｐｒであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of formula (III), (in formula, ^RV is

Is)

The alcohol product of formula (III) comprises a step of subjecting to oxidation in the presence of pyridinium chlorochromate and sodium chlorite, with the substrate represented by formula (II).

Formed during a cross-metathesis reaction between cis-octene-1-ol in the presence of a conformational ruthenium olefin metathesis catalyst represented by formula (I), where X is S and Y is. S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is i-Pr. R ⁶ is H, R ⁷ is H, R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, R ¹⁴ is i-Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, and so on. R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

（式中、Ｒ^ｚは

であり、少なくとも１つの炭素−炭素二重結合は、９５／５、又は９６／４、又は９７／３、又は９８／２、又は９９／１、又は＞９９／＜１のＺ／Ｅ選択性を有する）、
式（ＩＩＩ）のアルコール生成物を、（式中、Ｒ^Ｖは

である）

ピリジニウムクロロクロメート及び亜塩素酸ナトリウムの存在下での酸化に投入する工程を含み、式（ＩＩＩ）のアルコール生成物は、式（ＩＩ）によって表される基材と

シス−オクテン−１−オールとの間の、式（Ｉ）によって表される立体選択性ルテニウムオレフィンメタセシス触媒の存在下での交差メタセシス反応中に形成され、式中、ＸはＳであり、ＹはＳであり、ＺはＮであり、ＷはＯであり、Ｒ^１はＨであり、Ｒ^２はＨであり、Ｒ^３はＨであり、Ｒ^４はＨであり、Ｒ^５はＭｅであり、Ｒ^６はＨであり、Ｒ^７はＭｅであり、Ｒ^８はＨであり、Ｒ^９はＭｅであり、Ｒ^１０はＭｅであり、Ｒ^１１はＨであり、Ｒ^１２はＭｅであり、Ｒ^１３はＨであり、Ｒ^１４はＭｅであり、Ｒ^１５はＣｌであり、Ｒ^１６はＨであり、Ｒ^１７はＨであり、Ｒ^１８はＣｌであり、Ｒ^１９はｉ−Ｐｒであり、Ｒ^２０はＨであり、Ｒ^２１はＨであり、Ｒ^２２はＨであり、Ｒ^２３はＨであり、Ｒ^２４はＨである。 In one embodiment, the present invention is at least one delta ¹² represented by formula (IV) ^- provides a process for preparing prostaglandin J product,

(In the formula, R ^z is

And at least one carbon-carbon double bond has a Z / E selectivity of 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1. Has),
The alcohol product of formula (III), (in formula, ^RV is

Is)

The alcohol product of formula (III) comprises a step of subjecting to oxidation in the presence of pyridinium chlorochromate and sodium chlorite, with the substrate represented by formula (II).

Formed during a cross-metathesis reaction between cis-octene-1-ol in the presence of a stereoselective ruthenium olefin metathesis catalyst represented by formula (I), where X is S and Y Is S, Z is N, W is O, R ¹ is H, R ² is H, R ³ is H, R ⁴ is H, and R ⁵ is Me. Yes, R ⁶ is H, R ⁷ is Me, R ⁸ is H, R ⁹ is Me, R ¹⁰ is Me, R ¹¹ is H, and R ¹² is Me. , R ¹³ is H, R ¹⁴ is Me, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr. Yes, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H.

Experimental Chapters In the examples below, efforts have been made to ensure accuracy in the numbers used (eg, quantity, temperature, etc.), but some experimental errors and deviations should also be considered. Unless otherwise stated, temperature is in degrees Celsius and pressure is at or near atmospheric pressure. Examples are not intended to limit the invention described herein, but instead are provided as representative examples of catalytic compounds of the invention and methods that can be used in their preparation, and catalysts of the invention. Is provided as a representative example of the method of using.
Materials and methods

Unless otherwise stated in the specific procedure, the reaction was carried out in a flame-dried glass material under an argon atmosphere. All metathesis reaction, in Vacuum Atmospheres glovebox filled with _{N 2,} it was carried out in the absence of air. A common solvent was purified by passing it through a solvent purification column. Commercially available substrates were used as received. After sparging all solvents and substrates with Ar, they were placed in a glove box and filtered through basic alumina (Blockmann I) before use. The reaction progress was described as E.I. It was monitored by thin layer chromatography (TLC) using a Merck silica gel 60 F254 precoated plate (0.25 mm) and visualized by UV fluorescence quenching, potassium permanganate, or p-anisaldehyde staining. Siliconic Silicon Flash P60 Academic Silicon gel (particle size: 0.040-0.063 mm) was used for flash chromatography. Analytical Chiral HPLC with 254 mm visualization, Daicel Chemical Industries, Ltd. It was performed using an Agilent 1100 Series HPLC using a Crystall OD-H column (4.6 mm × 25 cm) obtained from. The analytical SFC has a visualization of 210 mm from Daicel Chemical Industries, Ltd. _{It was performed using a Mettler SFC supercritical CO 2} analysis chromatography system using a Cellalcel (IC) column (4.6 mm × 25 cm) obtained from. GC conversion data was obtained using an HP-5 capillary column using an Agilent 6850 FID gas chromatograph. ¹ H and ¹³ C NMR spectra can be viewed on a Varian Inova 500 spectrometer (500 MHz and 126 MHz, respectively), a Bruker AV III HD spectrometer with a Prodigy liquid nitrogen temperature cryoprobe (400 MHz and 101 MHz), or a Varian Mercury 300 spectrometer, respectively. Recorded on 300 MHz and 75 MHz) and _{reported for chemical shifts to residual CHCl 3} (δ7.26 and δ77.16 ppm, respectively). ^{1 1} H NMR spectrum data are reported as follows: chemical shift (δ ppm) (majority, coupling constant (Hz), integral). The abbreviations are used as follows: s = singlet, b = wide singlet, d = doublet, t = triplet, q = quadruple, quint = quintuple, m = compound multiplet.
Infrared (IR) spectra are recorded on a Perkin Elmer Paragon 1000 spectrometer using an undiluted sample on an ATR diamond and reported at ^{absorption frequency (cm -1).} High resolution mass spectrum HRMS was obtained from the Caltech Mass Spectrum Facility using fast atomic collisions (FAB ⁺ ), electrospray ionization (TOF ES ⁺ ), or electron impact (EI ^+). Optical rotation was measured with a Jasco P-2000 polarimeter using a cell at 589 nm and a pass length of 100 mm.

The following abbreviations are used herein.

In a nitrogen-filled glove box, cis-5-octene-1-ol (150 mg, 1.17 mmol, 8.0 equivalents) was dissolved in toluene (2 mL) in a 50 mL Schlenk flask and the catalyst Ru-4 (9). A solution of 9.9 mg, 11.7 μmol, 1 mol%) in THF (0.7 mL) was added. The Schlenk flask was sealed, removed from the glove box and then connected to high vacuum. The valve was gradually opened (Note: open slowly and stir well to avoid splashing). After stirring for 15 minutes, the flask was refilled with argon, sealed and returned to the glove box. The residue was diluted with THF (0.5 mL) and aliquots were taken for GC analysis (the conversion rate of the homodimerization step by GC analysis was> 98%). A solution of 11 [CAS 2135628-52-1] (53 mg, 0.146 mmol, 1.0 eq) in THF (0.5 mL) was added to the Schlenk flask and Ru-4 (6.2 mg, 7.3 μmol, 5 mol%) was added. ), An additional portion of a THF (0.3 mL) catalytic solution was added. The Schlenk flask was sealed and removed from the glove box. After stirring the reaction at 40 ° C. for 24 hours, a small amount of ethyl vinyl ether was added. The solvent was removed under reduced pressure. The residue was purified by flash chromatography (SiO ₂ , hexane / EtOAc 2: 1) to give 14 (60 mg, 95%,> 99: 1 Z / E).
TLC (3: 1 hexane / EtOAc): Rf = 0.23 (UV).
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.50 (ddd, J = 6.0, 2.6, 1.0 Hz, 1H), 6.59 (ddt, J = 8.3, 7. 0, 1.3 Hz, 1H), 6.33 (dd, J = 6.0, 1.8 Hz, 1H), 5.49 (dddt, J = 8.6, 7.2, 5.5, 1.5 Hz, 1H), 5.35 (dtt, J = 11.0, 8.4, 1.6 Hz, 1H), 3.84 (quint, J = 5.9 Hz, 1H), 3. 63 (t, J = 6.5 Hz, 2H), 3.46 (ddt, J = 11.0, 4.2, 2.2 Hz, 1H), 2.63 (dddd, J = 13.8, 6.5, 4.2, 1.5 Hz, 1H), 2.50-2.34 (m, 2H), 2.17 (dddd, J = 14.5, 9.4, 8.0, 1) .3 Hz, 1H), 2.07-1.97 (m, 2H), 1.60-1.51 (m, 2H), 1.47-1.34 (m, 6H), 1.32- 1.19 (m, 5H), 0.95-0.81 (m, 12H), 0.05 (s, 3H), 0.05 (s, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ): δ 196.5, 161.8, 138.8, 135.0, 132.7, 132.5, 125.4, 71.7, 62.9, 43. 6, 37.5, 37.5, 32.5, 32.0, 30.7, 27.2, 26.0, 25.8, 25, 1, 22.8, 18.2, 14.2 -4.2, -4.5.
FTIR (ATR): 3443, 2965, 2928, 2856, 1703, 1652, 1580, 1472, 1360, 1251, 1206, 1127, 1048, 1005, 975,866,834,806,773,726,664 cm ^-1 .
HRMS (TOF, ES ⁺ , m / z): C ₂₆ H ₄₇ O ₃ Si [M + H] ⁺ Calculated value: 435.3289, measured value: 435.3298.
[Α] ^D ₂₃ : + 83.5 ° (c = 1.0, CHCl ₃ ).

_{NMO · H 2} O (81 mg, 6 mmol, 10.0 eq) was added to 14 (26 mg, 0.06 mmol, 1.0 eq) MeCN (0.3 mL) agitated solution. Tetrapropylammonium perrutenate (2.1 mg, 6 μmol, 0.1 eq) _{was added until NMO · H 2} O was completely dissolved and the reaction was stirred at 23 ° C. for 3 hours. The solution was _{diluted with Et 2} O (5 mL), passed through a short pad of silica gel, concentrated and subjected to the next reaction without further purification.
The residue was dissolved in MeCN (1.0 mL) and cooled to 0 ° C. Hydrofluoric acid _{(H 2} O in 48 wt%, 0.2 mL) and MeCN (0.4 mL) solution was added dropwise. After stirring the solution at the same temperature for 30 minutes, saturated NaHCO ₃ solution (1.5 mL) and saline solution (1.5 mL) were added. The aqueous phase was extracted with EtOAc (5 x 5 mL). The combined organic phases were dried over magnesium sulphate, filtered and concentrated (not dried). The residue was purified by flash chromatography (SiO ₂ , CH ₂ Cl ₂ / MeOH 20: 1) to give 1 (18 mg, 89% over 2 steps) as a colorless liquid.
TLC (20: 1 CH ₂ Cl ₂ / MeOH): Rf = 0.14 (UV).
^{1 1} H NMR (500 MHz, CDCl ₃ ): δ 7.57 (ddd, J = 6.0, 2.6, 1.0 Hz, 1H), 6.58 (ddt, J = 8.4, 7. 2,1.3 Hz, 1H), 6.36 (dd, J = 6.0, 1.8 Hz, 1H), 5.54-5.38 (m, 2H), 3.86 (dtt, J) = 7.9, 6.4, 4.0 Hz, 1H), 3.47 (ddt, J = 9.5, 4.0, 2.1 Hz, 1H), 2.78-2.68 (m) , 1H), 2.57 (dt, J = 14.8, 6.8 Hz, 1H), 2.52-2.42 (m, 1H), 2.40-2.33 (m, 2H), 2.20-2.02 (m, 3H), 1.77-1.64 (m, 2H), 1.61-1.41 (m, 3H), 1.40-1.24 (m, 5H) ), 0.90 (t, J = 6.8 Hz, 3H).
¹³ C NMR (126 MHz, CDCl ₃ ): δ 196.6, 177.3, 162.0, 139.8, 135.0, 131.8, 131.7, 126.2, 71.5, 43. 9, 37.3, 36.7, 33.1, 31.9, 30.6, 26.6, 25.4, 24.6, 22.8, 14.2.
FTIR (ATR): 3445, 2960, 2929, 2858, 1699, 1646, 1579, 1463, 1406, 1265, 1237, 1135, 1084, 1033, 842, 810, 734,702 cm ^-1 .
HRMS (TOF, ES ⁺ , m / z): C ₂₀ H ₃₁ O ₄ [M + H] ⁺ Calculated value: 335.2217, measured value: 335.2223.
[Α] ^D ₂₃ : + 99.5 ° (c = 0.2, CHCl ₃ ).
Spectral data consistent with published data ( ^{1 1} H NMR, ¹³ C NMR, HRMS: Acharya, HP; Kobayashi, Y. Highly Effective Total Synthesis of Δ ^12- PGJ ₂ , 15-Deoxy-Δ ^{12, 14} − PGJ ₂ , and Their Analogues. Telehedran 2006, 62, 3329-3343.

In a nitrogen-filled glove box, cis-5-octene-1-ol (113 mg, 0.88 mmol, 8.0 eq) was dissolved in toluene (1 mL) in a 50 mL Schlenk flask and the catalyst Ru-4 (7). A solution of 5.5 mg, 8.8 μmol, mol%) in THF (0.6 mL) was added. The Schlenk flask was sealed, removed from the glove box and then connected to high vacuum. The valve was gradually opened (Note: open slowly and stir well to avoid splashing). After stirring for 15 minutes, the flask was refilled with argon, sealed and returned to the glove box. The residue was diluted with THF (0.5 mL) and aliquots were taken for GC analysis (the conversion rate of the homodimerization step by GC analysis was> 98%). A solution of 16 [CAS 2254448-24-1] (25 mg, 0.11 mmol, 1.0 eq) in THF (0.5 mL) was added to the Schlenk flask and Ru-4 (4.6 mg, 5.5 μmol, 5 mol%). ), An additional portion of a THF (0.2 mL) catalytic solution was added. The Schlenk flask was sealed and removed from the glove box. After stirring the reaction at 40 ° C. for 24 hours, a small amount of ethyl vinyl ether was added. The solvent was removed under reduced pressure. The residue was purified by flash chromatography (SiO ₂ , hexane / EtOAc 2: 1) to give 17 (31 mg, 93%,> 99: 1Z / E, 87% ee by chiral HPLC analysis).
TLC (4: 1 hexanes / EtOAc): Rf = 0.2 (UV).
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.48 (ddd, J = 6.0, 2.6, 1.0 Hz, 1H), 6.95 (dt, J = 11.0, 1.3) Hz, 1H), 6.35 (dd, J = 6.0, 1.8 Hz, 1H), 6.34-6.19 (m, 2H), 5.52-5.44 (m, 1H) , 5.38-5.30 (m, 1H), 3.63 (t, J = 6.5 Hz, 2H), 3.60-3.55 (m, 1H), 2.60 (dddd, J) = 14.0, 6.2, 4.3, 1.4 Hz, 1H), 2.30 (dtd, J = 14.4, 8.6, 1.2 Hz, 1H), 2.25-2 .17 (m, 2H), 2.01 (qd, J = 7.3, 1.4 Hz, 2H), 1.59-1.49 (m, 2H), 1.48-1.37 (m) , 5H), 1.34-1.29 (m, 4H), 0.89 (t, J = 7.0 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ): δ 197.6, 160.9, 147.0, 135.4, 135.3, 132.6, 131.8, 125.8, 125.3, 62. 9,43.7,33.6, 32.5, 31.5, 30.9, 28.6, 27.2, 25.8, 22.6, 14.2.
FTIR (ATR): 3445, 2960, 2930, 2862, 1690, 1629, 1580, 1447, 1264, 1207, 1054, 979, 732 cm ^-1 .
HRMS (TOF, ES ⁺ , m / z): _{Calculated value for C 20} H ₃₁ O ₂ [M + H] ⁺ : 303.2319, measured value: 303.2320.
[Α] ^D ₂₃ : +115.8 ° (c = 0.5, CHCl ₃ ).
HPLC conditions: 10% IPA, 1.0 mL / min, Chiralcel OD-H column, λ = 254 nm, tR (min): large = 10.12, small = 13.57.

_{NMO · H 2} O (65 mg, 0.46 mmol, 10.0 eq) was added to 17 (14 mg, 0.046 mmol, 1.0 eq) MeCN (0.5 mL) agitated solution. Tetrapropylammonium perruthenate (1.7 mg, 4.6 [mu] mol, 0.1 eq) was added to a NMO · _{H 2} O is completely dissolved and the reaction was stirred for 3 hours at 23 ° C.. The reaction mixture was stirred for 3 hours and the solvent was removed in vacuo. The residue was loaded onto a silica gel column, with _CH 2 Cl _2, then _{CH 2 Cl 2 / MeOH (20} : 1) and flushed with. 15-Deoxy-Δ ^12,14 -prostaglandin J ₂ (2) was obtained as a colorless oil (10 mg, 68% yield).
TLC (100% EtOAc): Rf = 0.70 (UV).
^{1 1} H NMR (400 MHz, CDCl ₃ ): δ 7.47 (ddd, J = 6.0, 2.6, 1.0 Hz, 1H), 6.95 (d, J = 11.0 Hz, 1H) ), 6.38-6.35 (m, 1H), 6.33-6.20 (m, 2H), 5.50-5.33 (m, 2H), 3.59 (ddd, J = 8) .4, 4.1, 2.2 Hz, 1H), 2.59 (m, 1H), 2.36-2.19 (m, 5H), 2.05 (q, J = 7.3 Hz, 2H), 1.68 (quint, J = 7.5 Hz, 2H), 1.50-1.41 (m, 2H), 1.34-1.28 (m, 4H), 0.90 (t) , J = 7.0 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ): δ 197.6, 177.9, 160.8, 147.2, 135.5, 135.1, 131.9, 131.5, 126.2, 125. 8, 43.6, 33.6, 33.2, 31.6, 30.8, 28.6, 26.7, 24.6, 22.6, 14.2.
FTIR (ATR): 2960, 2928, 2850, 1708, 1692, 1629, 1456, 1265, 1207, 978, 734,703 cm-1.
HRMS (TOF, ES +, m / z): C ₂₀ H ₂₉ O ₃ [M + H] ⁺ Calculated value: 317.2111, measured value: 317.2127.
[Α] ^D ₂₃ : + 106.2 ° (c = 0.2, CHCl ₃ ).
Spectral data consistent with published data ( ^{1 1} H NMR, ¹³ C NMR, HRMS):
Acharya, H. et al. P. Kobayashi, Y. et al. Highly Effective Total Synthesis of Δ12-PGJ ₂ , 15-Deoxy-Δ ^{12, 14-} PGJ ₂ , and Their Analogues. Tetrahedron 2006, 62, 3329-3343.
Brummondo, K. et al. M. Sill, P. et al. C. Chen, H. et al. The First Total Synthesis of 15-Deoxy-Δ ^12,14- Prostaglandin J ₂ and the Unambiguous Assignment of the C14 Stereochemistry. Org. Lett. 2004, 6, 149-152.
Kim, N.M. -J. Moon, H. et al. Park, T. et al. Yun, H. et al. Jung, J. et al. -W. Chang, D.C. -J. Kim, D.I. -D. Shu, Y. et al. -G. Concise and Enantioselective Total Synthesis of 15-Deoxy-Δ ^{12, 14-} Prostaglandin J ₂ . J. Org. Chem. 2010, 75, 7458-7460.
Egger, J. et al. Fischer, S.A. Brettcher, P. et al. Freigan, S.A. Kopf, M. et al. Carreira, E.I. M. Total Synthesis of Prostaglandin 15d-PGJ ₂ and Investment of Its Effect on the Selection of IL-6 and IL-12. Org. Lett. 2015, 17, 4340-4343.

In a nitrogen-filled glove box, cis-5-octene-1-ol (72 mg, 0.55 mmol, 6.7 equivalents) was dissolved in toluene (1 mL) in a 50 mL Schlenk flask and the catalyst Ru-4 (4). A solution of 0.7 mg, 5.6 μmol, 1 mol%) in THF (0.6 mL) was added. The Schlenk flask was sealed, removed from the glove box and then connected to high vacuum. The valve was gradually opened (Note: open slowly and stir well to avoid splashing). After stirring for 15 minutes, the flask was refilled with argon, sealed and returned to the glove box. The residue was diluted with 0.5 mL of THF and aliquots were taken for GC analysis (the conversion rate of the homodimerization step by GC analysis was> 98%). Add a 0.5 mL THF solution of 22 [CAS 2254448-26-3] (30 mg, 0.083 mmol, 1 eq) to a Schlenk flask and have Ru-4 (2.9 mg, 3.5 μmol, 5 mol%). 4 mL of additional catalytic solution was added. The Schlenk flask was sealed and removed from the glove box. After stirring the reaction at 23 ° C. for 12 hours, a small amount of ethyl vinyl ether was added. The solvent was removed under reduced pressure. The residue was purified by flash chromatography (hexane / EtOAc 10: 1-2: 1). Twenty-three (16 mg, 44%) and 24 (8 mg, 31%) were isolated as two products.
Compound 23:
TLC (2: 1 hexanes / EtOAc): Rf = 0.28 (UV).
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.50 (ddd, J = 6.0, 2.7, 1.0 Hz, 1H), 6.60 (ddt, J = 8.2,7.0 , 1.3 Hz, 1H), 6.32 (dd, J = 6.0, 1.8 Hz, 1H), 5.53-5.43 (m, 2H), 5.41-5.31 ( m, 2H), 3.89 (quint, J = 6.1 Hz, 1H), 3.64 (t, J = 6.5 Hz, 2H), 3.45 (ddq, J = 8.4,4) .3, 2.2 Hz, 1H), 2.68-2.55 (m, 1H), 2.43 (ddd, J = 7.7, 6.4, 2.3 Hz, 2H), 2. 29-2.11 (m, 3H), 2.08-1.91 (m, 4H), 1.62-1.51 (m, 2H), 1.48-1.36 (m, 2H), 0.94 (t, J = 7.6 Hz, 3H), 0.88 (s, 9H), 0.06 (s, 3H), 0.05 (s, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ) δ 196.5, 161.8, 138.9, 135.0, 134.2, 132.7, 132.5, 125.5, 124.4, 71.7 , 62.9, 43.6, 37.0, 35.3, 32.5, 30.8, 27.2, 26.0, 25.9, 20.9, 18.2, 14.3- 4.4, -4.4.
FTIR (ATR): 3429, 2965, 2928, 2856, 2361, 327, 1702, 1652, 1580, 1472, 1360, 1251, 1213, 1066, 1005, 968, 834,807, 774, 721, 668 cm ^-1 .
HRMS (FAB ⁺ , m / z): C ₂₆ H ₄₅ O ₃ Si [M + H] ⁺ Calculated value: 433.3132, measured value: 433.3121.
[Α] ^D ₂₃ : +136.3 ° (c = 1.0, C ₆ H ₆ ).
Compound 24:
TLC (2: 1 hexanes / EtOAc): Rf = 0.6 (UV).
^{1 1} H NMR (400 MHz, CDCl ₃ ): δ 7.43 (ddd, J = 5.9, 2.8, 1.0 Hz, 1H), 6.80 (ddt, J = 10.8, 8. 8,1.3 Hz, 1H), 6.31 (dd, J = 5.9, 1.7 Hz, 1H), 5.76 (q, J = 9.1 Hz, 1H), 5.61 ( ddddd, J = 11.9, 10.7, 5.2, 1.2 Hz, 1H), 4.08-4.02 (m, 1H), 3.27 (d, J = 9.6 Hz, 1H), 2.38 (dd, J = 9.5,3.0 Hz, 2H), 2.24 (q, J = 11.6 Hz, 2H), 2.17-1.95 (m, 2H) ), 0.91 (s, 9H), 0.11 (s, 3H), 0.08 (s, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ): δ 196.4, 162.3, 141.3, 134.0, 132.4, 130.6, 129.6, 73.1, 44.2, 34. 7,34.5, 32.6, 26.0, 18.3, -4.6, -4.7.
FTIR (ATR): 2952, 2926, 2886, 2855, 2359, 2339, 1705, 1654, 1586, 1471, 1369, 1251, 1190, 1077, 1039, 997, 980, 938, 855, 835, 808, 790, 774 , 727,668 cm ^-1 .
HRMS (FAB ⁺ , m / z): C ₁₈ H ₂₉ O ₂ Si [M + H] ⁺ Calculated value: 305.1931, measured value: 305.1942.
[Α] ^D ₂₃ : −27.8 ° (c = 0.8, CHCl ₃ )

Preparation of alcohol 23 in the presence of Ru-2

In a nitrogen-filled glove box, 22 (64 mg, 0.18 mmol, 1.0 eq) and 5-hexen-1-ol (142 mg, 1.42 mmol, 8.0 eq) were weighed into a 4 mL vial. THF (0.3 mL) was added to dissolve the mixture. The catalyst Ru-2 (24 mg, 20 mol%) was dissolved in THF (0.4 mL) and 0.1 mL of this catalyst solution was transferred to a vial. The vial was sealed with a 14/20 septum and removed from the glove box. The reaction was stirred at 40 ° C. using an argon stream (saturated with anhydrous THF) bubbling through a needle. A portion of the catalytic solution (0.1 mL) was added to the vial for 1 hour each. After adding all catalysts, the reaction mixture was continuously stirred with argon bubbling for 4 hours. A few drops of ethyl vinyl ether were added and the reaction mixture was concentrated in vacuo. The residue was purified by column chromatography (SiO ₂ , hexane / EtOAc 2: 1) to give 23 (40 mg, 52%) as a colorless liquid. Compound 26 was the proposed by-product (as measured by crude NMR analysis, the molar ratio of 23:26 was 32: 1).
Compound 23: The characterization data was consistent with previously obtained data.
Compound 26: Characteristic data not available due to difficulty in separation are ^{calculated for LC-MS (TOF, ES +} , m / z): C ₂₄ H ₄₁ O ₃ Si [M + H] ⁺ : 405. 2819, measured value: 405.2801.

_{NMO · H 2} O (67.5 mg, 0.5 mmol, 10.0 eq) was added to 23 (21.6 mg, 0.05 mmol, 1.0 eq) MeCN (0.5 mL) agitated solution. Tetrapropylammonium perrutenate (1.8 mg, 5 μmol, 0.1 eq) _{was added until NMO · H 2} O was completely dissolved and the reaction was stirred at 23 ° C. for 3 hours. The solution was _{diluted with Et 2} O (5 mL), passed through a short pad of silica gel, concentrated and subjected to the next reaction without further purification.
The residue was dissolved in MeCN (1.0 mL) and cooled to 0 ° C. Hydrofluoric acid _{(H 2} O in 48 wt%, 0.2 mL) and MeCN (0.4 mL) solution was added dropwise. After stirring the solution at the same temperature for 30 minutes, saturated NaHCO ₃ solution (1.5 mL) and saline solution (1.5 mL) were added. The aqueous phase was extracted with EtOAc (5 x 5 mL). The combined organic phases were dried over magnesium sulphate, filtered and concentrated (not dried). The residue was purified through flash chromatography (SiO ₂ , CH ₂ Cl ₂ / MeOH 20: 1) and BiotageR SNAP Ultra C18 column (H ₂ O / MeOH) to give 3 (10 mg, 60% over 2 steps) as a colorless liquid. Obtained.
TLC (100% EtOAc): Rf = 0.55 (UV).
¹ H NMR (400 MHz, CDCl ₃ ): δ 7.58 (ddd, J = 6.0, 2.6, 1.0 Hz, 1H), 6.57 (ddt, J = 8.4, 7. 0, 1.2 Hz, 1H), 6.36 (dd, J = 6.0, 1.8 Hz, 1H), 5.69-5.60 (m, 1H), 5.60-5.45 (M, 2H), 5.45-5.35 (m, 1H), 3.91 (quint, J = 6.8 Hz, 1H), 3.50-3.44 (m, 1H), 2. 75 (ddd, J = 13.9, 6.9, 4.4 Hz, 1H), 2.68-2.58 (m, 1H), 2.49 (ddd, J = 15.2, 8.4) , 7.0 Hz, 1H), 2.36 (t, J = 6.8 Hz, 2H), 2.33-2.28 (m, 2H), 2.20-1.98 (m, 5H) , 1.68 (quint, J = 7.0 Hz, 2H), 0.96 (t, J = 7.5 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ): δ 196.4, 175.8, 161.8, 139.9, 136.4, 135.1, 131.7, 131.2, 126.3, 123. 6,71.1,44.0,36.3,34.5,32.9,30.7,26.6,24.7,20.9,14.4.
FTIR (ATR): 3449, 3010, 2965, 2919, 2850, 1728, 1703, 1650, 1579, 1455, 1375, 1222, 1182, 1046, 959, 838, 809, 721 cm-1.
HRMS (FAB ⁺ , m / z): C ₂₀ H ₂₉ O4 [M + H] ^{Calculated value for +} : 333.2060, measured value: 333.2060.
[Α] ^D ₂₃ : + 122.6 ° (c = 0.5, C ₆ H ₆ ).
Published data (6 natural and synthetic delta ¹² - prostaglandin _J 3 (3) of the ¹ H Comparison of the NMR data) and matching spectral data ^{(1 H NMR, 13 C NMR} , HRMS) is, J. Am. Chem. It is published in Table S2 of. Soc. ，

In a nitrogen-filled glove box, cis-5-octene-1-ol (205 mg, 1.6 mmol, 8.0 equivalents) was dissolved in toluene (1 mL) in a 50 mL Schlenk flask and the catalyst Ru-4 (13). A solution of 0.6 mg, 16 μmol, 1 mol%) in THF (0.6 mL) was added. The Schlenk flask was sealed, removed from the glove box and then connected to high vacuum. The valve was gradually opened (Note: open slowly and stir well to avoid splashing). After stirring for 15 minutes, the flask was refilled with argon, sealed and returned to the glove box. The residue was diluted with 0.5 mL of THF and aliquots were taken for GC analysis (the conversion rate of the homodimerization step by GC analysis was> 98%). A 0.5 mL THF solution of 28 [CAS 2254448-29-6] (46 mg, 0.2 mmol, 1.0 eq) was added to the Schlenk flask and 0. 4 mL of additional catalytic solution was added. The Schlenk flask was sealed and removed from the glove box. After stirring the reaction at 23 ° C. for 12 hours, a small amount of ethyl vinyl ether was added. The solvent was removed under reduced pressure. The residue was purified by column chromatography (SiO ₂ , hexane / EtOAc 2: 1). Compounds 29 (22 mg, 36%) and 30 were separated as a mixture (28 mg, 29:30 molar ratio was 3: 1 as measured by crude NMR analysis).
Compound 29: Due to difficulty in separation, characterization data are not available.
The mass data is the calculated value for LC-MS (TOF, ES ⁺ , m / z): C ₂₀ H ₂₉ O ₂ [M + H] ⁺ : 301.1622, and the measured value: 301.2080. Obtained by
Compound 30: Characteristic data not available due to difficulty in separation are ^{calculated for LC-MS (TOF, ES +} , m / z): C ₁₈ H ₂₅ O ₂ [M + H] ⁺ : 273.1849. , Measured value: Obtained by 273.1759.

Preparation of alcohol 29 in the presence of Ru-2

In a nitrogen-filled glove box, 28 (23 mg, 0.1 mmol, 1.0 eq) and 5-hexen-1-ol (80 mg, 0.8 mmol, 8.0 eq) were weighed into a 4 mL vial. THF (0.1 mL) was added to dissolve the mixture. The catalyst Ru-2 (13.6 mg, 20 mol%) was dissolved in THF (0.4 mL) and 0.1 mL of this catalyst solution was transferred to a vial. The vial was sealed with a 14/20 septum and removed from the glove box. The reaction was stirred at 40 ° C. using an argon stream (saturated with anhydrous THF) bubbling through a needle. A portion of the catalytic solution (0.1 mL) was added to the vial for 1 hour each. After adding all catalysts, the reaction mixture was continuously stirred with argon bubbling for 2 hours. A few drops of ethyl vinyl ether were added and the reaction mixture was concentrated in vacuo. The residue was purified by column chromatography (SiO ₂ , hexane / EtOAc 2: 1). Compounds 29 (9.2 mg, 31%) and 30 were separated as a mixture (12 mg, as measured by crude NMR analysis, the molar ratio of 29:30 was 3: 1.
Compound 29: Due to difficulty in separation, characterization data are not available. The mass data is calculated for LC-MS (TOF, ES ⁺ , m / z): C ₁₈ H ₂₅ O ₂ [M + H] ⁺ : 273.1849, measured value: 273.1855. Obtained by

_{Pyridinium chlorochromate (22 mg, 0.1 mmol, 3.0 eq) in a CH 2} Cl ₂ (0.5 mL) solution of 29 (mixed with by-product 30) (10 mg, 0.033 mmol, 1.0 eq). , 23 ° C. The reaction was monitored by TLC, stirred for 3 hours _{and then diluted with Et 2} O (3 mL). The resulting solution was filtered through a short pad of silica gel and subjected to the next step without further purification. The residue was dissolved in t-BuOH (0.5 mL) at 23 ° C. to 2-methyl-2-butene (35 μL, 0.33 mmol, 10 eq), NaH ₂ PO ₄ · H ₂ O (6.9 mg, 0). .05 mmol, 1.5 eq) H ₂ O (0.12 mL) solution and NaCl O ₂ (80%, 5.6 mg, 0.05 mmol, 1.5 eq) H ₂ O (0.12 mL) solution. Added continuously. After stirring at 23 ° C. for 30 minutes, the reaction mixture _{was diluted with a solution of NaH 2} PO ₄ · H ₂ O (108 mg) in H ₂ O (2 mL) and extracted with EtOAc (5 × 5 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Pure compound 4 (4 mg, 0.) as a colorless oil by purification through flash column chromatography (SiO ₂ , CH ₂ Cl ₂ / MeOH 20: 1) and Biotage R SNAP Ultra C18 column (H _{2 O / MeOH).} 013 mmol, 28 yield 12%) was obtained.
TLC (10: 1 CH ₂ Cl ₂ / MeOH): Rf = 0.44 (UV).
^{1 1} H NMR (500 MHz, CDCl ₃ ): δ 7.48 (ddd, J = 6.1,2.6, 1.0 Hz, 1H), 6.96 (d, J = 11.5 Hz, 1H) ), 6.42-6.31 (m, 2H), 6.22 (dt, J = 14.9, 6.3 Hz, 1H), 5.57-5.51 (m, 1H), 5. 50-5.43 (m, 1H), 5.37 (dtt, J = 10.1, 6.8, 1.7 Hz, 2H), 3.64-3.55 (m, 1H), 2. 98 (t, J = 6.8 Hz, 2H), 2.60 (dt, J = 12.3, 5.9 Hz, 1H), 2.43-2.25 (m, 3H), 2.12. -2.00 (m, 4H), 1.69 (quint, J = 7.4 Hz, 2H), 0.99 (t, J = 7.5 Hz, 3H).
¹³ C NMR (101 MHz, CDCl ₃ ): δ 197.6, 176.6, 160.9, 144.5, 135.5, 135.5, 134.2, 131.6, 131.5, 126. 1,125.8, 124.6, 43.6, 33.0, 31.2, 30.9, 26.7, 24.6, 20.7, 14.3.
FTIR (ATR): 3010, 2960, 2926, 2874, 2854, 1710, 1693, 1626, 1578, 1512, 1455, 1208, 1154, 1087, 1024, 977, 817, 728 cm ^-1 .
HRMS (FAB +, m / z): C ₂₀ H ₂₇ O ₃ [M + H] ⁺ Calculated value: 315.1955, measured value: 315.1968.
[Α] ^D ₂₃ : +129.6 ° (c = 0.07, C ₆ H ₆ ).
Spectral data consistent with published data ( ^{1 1} H NMR, ¹³ C NMR, HRMS):
Nicolaou, K. Nicola C. Pulukuri, K. et al. K. Rigol, S. et al. Heretsch, P. et al. Yu, R.M. Grove, C.I. I. Hale, C.I. R. H. El Marroni, A. et al. Fets, V.I. Bronstrup, M. et al. Aujay M.M. Sandoval J. et al. Gavrilliuk J. et al. Synthesis and Biological Investigation of Δ ¹² − Prostaglandin J ₃ (Δ ^{12 −} PGJ ₃ ) Analogues and Related Compounds. J. Am. Chem. Soc. 2016, 138, 6550-6560.

Claims (10)

At least one delta ¹² represented by formula (IV) ^- A method for the production of prostaglandin J product,

(In the formula, R ^z is

Selected from, at least one carbon-carbon double bond is 95/5, or 96/4, or 97/3, or 98/2, or 99/1, or> 99 / <1 Z / E selection. The alcohol product of formula (III),

The alcohol product of formula (III) comprises subjecting to oxidation conditions with a substrate represented by formula (II).

Formed during a cross-metathesis reaction with cis-octene-1-ol in the presence of a ruthenium olefin metathesis catalyst, in the formula, ^Rv is:

The method to choose from. The ruthenium catalyst is a steric retention ruthenium olefin metathesis catalyst represented by the formula (I).

X is O or S,
Y is O or S,
Z is N or CR ³²
W is O, halogen, NR ³³ or S.
R ¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 2} , or polycyclic with ^{R 3} or with R ^4. You may form a formula ring,
R ² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 1} , or polycyclic with ^{R 3} or with R ^4. You may form a formula ring,
R ³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or may form a polycyclic ring with ^{R 2} or with R ^{1 , or R 4} May form a spiro compound with
R ⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 3} , or polycyclic with ^{R 2} or with R ^1. You may form a formula ring,
R ⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to} C ₂₄ aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁶ to form an optionally substituted polycyclic ring.
R ⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together or R ⁷ together with R ^5, may form a polycyclic ring which is optionally substituted,
R ⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ⁶ or with R ^8, may form a polycyclic ring which is optionally substituted,
R ⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ⁷ or with R ^9, may form a polycyclic ring which is optionally substituted,
R ⁹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁸ may form an optionally substituted polycyclic ring.
R ¹⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹¹ may form an optionally substituted polycyclic ring.
R ¹¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ¹⁰ or together with R ^12, may form a polycyclic ring which is optionally substituted,
R ¹² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ¹¹ or together with R ^13, may form a polycyclic ring which is optionally substituted,
R ¹³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ¹⁴ or together with R ^12, may form a polycyclic ring which is optionally substituted,
R ¹⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹³ may form a polycyclic ring.
R ¹⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹⁶ may form an optionally substituted polycyclic ring.
R ¹⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} substituted aryl, or an optionally C _{3 to 8} substituted cycloalkenyl, or together with R ¹⁵ or together with R ^17, may form a polycyclic ring which is optionally substituted ,
R ¹⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} substituted aryl, or an optionally C _{3 to 8} substituted cycloalkenyl, or together with R ¹⁸ or together with R ^16, may form a polycyclic ring which is optionally substituted ,
R ¹⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or with R ¹⁷ may form an optionally substituted polycyclic ring.
R ¹⁹ is H, optionally substituted C _1-24 alkyl, -C (R ³⁴ ) (R ³⁵ ) COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O) H, -C (R). ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , -C (O) R ²⁵ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, Arbitrarily substituted C _{5 to 24} aryl, optionally substituted C _{3 to 8} cycloalkenyl, or with R ³³ may form an optionally substituted heterocycle, or W is a halogen. If is zero,
R ²⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ may form a polycyclic ring.
R ²¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²⁰ or with R ²² may form a polycyclic ring.
R ²² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ or with R ²³ may form a polycyclic ring.
R ²³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²² may form a polycyclic ring.
R ²⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl.
R ²⁵ was OH, OR ³⁰ , NR ²⁷ R ²⁸ , optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted. C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl,
R ²⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁷ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁹ is H, optionally substituted C _{1 to 24} alkyl, OR ²⁶ , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted. C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl.
R ³⁰ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally substituted. C _3-8 cycloalkenyl,
R ³¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³³ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, optionally. It may be a substituted C _3-8 cycloalkenyl or, ^{together with R 19} , form an arbitrarily substituted heterocycle.
R ³⁴ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁵ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁷ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally substituted. C _3-8 cycloalkenyl,
R ³⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴⁰ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
The method of claim 1, wherein x is 1 or 2. The ruthenium catalyst is a Z-selective ruthenium olefin metathesis catalyst represented by the formula (V).

During the ceremony
W is O, halogen, NR ³³ or S.
X ¹ is hydrogen, halide, nitrate, optionally substituted C _{1 to} C ₂₀ alkyl, optionally substituted C _{5 to} C ₂₄ aryl, optionally substituted C _{1 to} C ₂₀ alkoxy, optionally substituted. C _{1 to} C ₂₀ alkyl carboxylates, optionally substituted C _{5 to} C ₂₄ aryloxy, optionally substituted C _{2 to} C ₂₀ alkoxycarbonyl, optionally substituted C _{6 to} C ₂₄ aryloxycarbonyl , Arbitrarily substituted C _{6 to} C ₂₄ arylcarboxylate, optionally substituted C _{2 to} C ₂₄ acyl, optionally substituted C _{2 to} C ₂₄ acyloxy, optionally substituted C _{1 to} C ₂₀ alkyl Alkoxy, optionally substituted C _{5 to} C ₂₄ aryl sulfonate, optionally substituted C _{1 to} C ₂₀ alkylsulfanyl, optionally substituted C _{5 to} C ₂₄ aryl sulfanyl, optionally substituted C _{1 to} C ₂₀ alkylsulfinyl, or a _C 5 _{-C 24} arylsulfinyl optionally substituted,
R ¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 2} , or polycyclic with ^{R 3} or with R ^4. You may form a formula ring,
R ² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 1} , or polycyclic with ^{R 3} or with R ^4. You may form a formula ring,
R ³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl, or may form a polycyclic ring with ^{R 2} or with R ^{1 , or R 4} May form a spiro compound with
R ⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or spiro compounds may be formed with ^{R 3} , or polycyclic with ^{R 2} or with R ^1. You may form a formula ring,
R ⁵ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁶ may form an optionally substituted polycyclic ring.
R ⁶ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional has been C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted substituted, or together or R ⁷ together with R ^5, may form a polycyclic ring which is optionally substituted,
R ⁷ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ⁶ or with R ^8, may form a polycyclic ring which is optionally substituted,
R ⁸ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional a substituted C _{5 to 24} aryl, or a C _{3 to 8} cycloalkenyl optionally substituted, or together with R ⁷ or with R ^9, may form a polycyclic ring which is optionally substituted,
R ⁹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ⁸ may form an optionally substituted polycyclic ring.
R ¹⁹ is H, optionally substituted C _1-24 alkyl, -C (R ³⁴ ) (R ³⁵ ) COOR ³⁶ , -C (R ³⁴ ) (R ³⁵ ) C (O) H, -C (R). ³⁴ ) (R ³⁵ ) C (O) R ³⁷ , -C (R ³⁴ ) (R ³⁵ ) CR ³⁸ (OR ³⁹ ) (OR ⁴⁰ ), -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ R ⁴² , -C (R ³⁴ ) (R ³⁵ ) C (O) NR ⁴¹ OR ⁴⁰ , -C (O) R ²⁵ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, Arbitrarily substituted C _{5 to 24} aryl, optionally substituted C _{3 to 8} cycloalkenyl, or with R ³³ may form an optionally substituted heterocycle, or W is a halogen. If is zero,
R ²⁰ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ may form a polycyclic ring.
R ²¹ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²⁰ or with R ²² may form a polycyclic ring.
R ²² is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²¹ or with R ²³ may form a polycyclic ring.
R ²³ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, optionally substituted C _{3 to 8} cycloalkenyl, or with R ²² may form a polycyclic ring.
R ²⁴ is H, optionally substituted C _1-24 alkyl, halogen, -C (O) R ²⁵ , -OR ²⁶ , CN, -NR ²⁷ R ²⁸ , NO ₂ , -CF ₃ , -S (O). ) _X R ²⁹ , -P (O) (OH) ₂ , -OP (O) (OH) ₂ , -SR ³¹ , optionally substituted heterocycle, optionally substituted C _3-8 cycloalkyl, optional C _{5 to 24} aryl substituted with, or optionally substituted C _{3 to 8} cycloalkenyl.
R ²⁵ was OH, OR ³⁰ , NR ²⁷ R ²⁸ , optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted. C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl,
R ²⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁷ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ²⁹ is H, optionally substituted C _{1 to 24} alkyl, OR ²⁶ , -NR ²⁷ R ²⁸ , optionally substituted heterocycle, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted. C _{5 to 24} aryl, or optionally substituted C _{3 to 8} cycloalkenyl.
R ³⁰ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally substituted. C _3-8 cycloalkenyl,
R ³¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³³ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, optionally. It may be a substituted C _3-8 cycloalkenyl or, ^{together with R 19} , form an arbitrarily substituted heterocycle.
R ³⁴ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁵ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁶ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁷ is optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally substituted. C _3-8 cycloalkenyl,
R ³⁸ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ³⁹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴⁰ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴¹ is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
R ⁴² is H, optionally substituted C _{1 to 24} alkyl, optionally substituted C _{3 to 8} cycloalkyl, optionally substituted heterocycle, optionally substituted C _{5 to 24} aryl, or optionally. _{C 3-8} cycloalkenyl substituted with
The method of claim 1, wherein x is 1 or 2. The method of claim 1, wherein the oxidation occurs in the presence of tetrapropylammonium perlutenate and 4-methylmorpholine N-oxide monohydrate. The method of claim 1, wherein the oxidation occurs in the presence of pyridinium chlorochromate and sodium chlorite. R ^z

And R ^v is

The ruthenium catalyst is a steric retention catalyst represented by the formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, and so on. R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, and R ¹⁴ is i. -Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H, the method of claim 4. R ^z

And R ^v is

The ruthenium catalyst is a Z-selective catalyst represented by the formula (V), in which W is O, X ¹ is nitrate, R ¹ is H, and R ² is H. R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, R ⁸ is H, and R ⁹ is. i-Pr, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H. The method according to claim 4. R ^z

And R ^v is

The ruthenium catalyst is a steric retention catalyst represented by the formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, and so on. R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, and R ¹⁴ is i. -Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H, the method of claim 5. R ^z

And R ^v is

The ruthenium catalyst is a Z-selective catalyst represented by the formula (V), in which W is O, X ¹ is nitrate, R ¹ is H, and R ² is H. R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, R ⁸ is H, and R ⁹ is. i-Pr, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H. The method according to claim 5. R ^z

And R ^v is

The ruthenium catalyst is a steric retention catalyst represented by the formula (I), in which X is S, Y is S, Z is N, W is O, and R. ¹ is H, R ² is H, R ³ is H, R ⁴ is H, R ⁵ is i-Pr, R ⁶ is H, R ⁷ is H, and so on. R ⁸ is H, R ⁹ is i-Pr, R ¹⁰ is i-Pr, R ¹¹ is H, R ¹² is H, R ¹³ is H, and R ¹⁴ is i. -Pr, R ¹⁵ is Cl, R ¹⁶ is H, R ¹⁷ is H, R ¹⁸ is Cl, R ¹⁹ is i-Pr, R ²⁰ is H, R ²¹ is H, R ²² is H, R ²³ is H, and R ²⁴ is H, the method of claim 5.